Process, apparatus, and system for recovering materials from batteries

ABSTRACT

An apparatus for carrying out size reduction of battery materials under immersion conditions can include a housing configured to hold an immersion liquid comprising at least one of sodium hydroxide and calcium hydroxide. A first feed chute may define an opening therein for receiving battery materials of a first type into the housing and a first submergible comminuting device may be disposed within the housing and submerged in the immersion liquid to receive the battery materials of the first type from the first feed chute. The first submergible comminuting device may be configured to cause a size reduction of the battery materials of the first type to form a first reduced-size battery material.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 16/912,243 filed Jun. 25, 2020, which is a continuation of U.S.patent application Ser. No. 16/461,158 filed May 15, 2019, which is anational stage entry of international patent application no.PCT/CA2018/050640 filed May 30, 2018, which claimed priority to U.S.provisional applications 62/669,205 and 62/512,460 filed May 9, 2018 andMay 30, 2017 respectively; the entirety of these applications beingincorporated herein by reference.

FIELD OF THE APPLICATION

The present application pertains to the field of battery recycling. Moreparticularly, the present application relates to a process, apparatus,and system for recovering materials from batteries, in particularrechargeable lithium-ion batteries.

INTRODUCTION

Lithium-ion rechargeable batteries are increasingly powering automotive,consumer electronic, and industrial energy storage applications.However, approximately less than 5% of produced spent lithium-ionbatteries are recycled globally, equivalent to approximately 70,000tonnes of spent lithium-ion batteries recycled/year. In contrast, anestimated 11+ million tonnes of spent lithium-ion battery packs areexpected to be discarded between 2017 and 2030, driven by application oflithium-ion batteries in electro-mobility applications such as electricvehicles.

Such spent lithium-ion battery packs have a valuable content of cobalt,lithium, copper, graphite, nickel, aluminum, manganese, etc.; and thus,spent lithium-ion battery packs can be viewed as a high grade ‘urbanmining’ source of lithium and many other valuable metals. However,current lithium-ion battery recycling processes consist of, for example,smelting or pyrometallurgy that primarily recovers metal alloys(typically cobalt, copper, and/or nickel). Via pyrometallurgy, lithiumin the spent lithium-ion batteries is lost in the slag and/or off-gasstreams from a smelter's furnace(s), for example. The slag is generallysold to the construction industry for use as road base, for example, andthe lithium is unrecoverable economically.

As such, the quantities and valuable contents of spent lithium-ionbatteries will require waste diversion industries to adapt; for example,to emulate lead acid battery recycling industries, where approximatelymore than 90% of spent lead acid batteries are recycled in manyjurisdictions globally.

Advanced lithium-ion battery recycling processes could offer an economicand environmental opportunity. For example, the estimated 11+ milliontonnes of spent battery packs contain approximately US$65 billion ofresidual value in metals and other components. Further, recyclinglithium-ion batteries could reduce greenhouse gas emissions globally byapproximately 1.2 billion equivalent tonnes of CO₂ between 2017 and 2040by providing an offset against/reducing the amount of raw materialderived from primary sources (i.e. mining, refining); and, potentiallyprevent metals (e.g., heavy metals) and materials from spent lithium-ionbatteries being landfilled.

The above information is provided for the purpose of making knowninformation believed by the applicant to be of possible relevance to thepresent application. No admission is necessarily intended, nor should beconstrued, that any of the preceding information constitutes prior artagainst the present application.

SUMMARY OF THE APPLICATION

As noted in further detail below, rechargeable lithium-ion batteriescomprise a number of different materials. “Black mass” is known to be acomponent of rechargeable lithium-ion batteries, which comprises acombination of cathode and/or anode electrode powders comprising lithiummetal oxides and lithium iron phosphate (cathode) and graphite (anode).Materials present in rechargeable lithium-ion batteries include organicssuch as alkyl carbonates (e.g. C₁-C₆ alkyl carbonates, such as ethylenecarbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC),diethyl carbonate (DEC), propylene carbonate (PC), and mixturesthereof), iron, aluminum, copper, plastics, graphite, cobalt, nickel,manganese, and of course lithium. Recovering such materials fromrechargeable lithium-ion batteries is highly desirable.

Thus, in accordance with an aspect of the present application, there isprovided a process for recovering materials from rechargeablelithium-ion batteries comprising:

-   -   i) processing lithium-ion batteries to form a size-reduced feed        stream;    -   ii) separating the size-reduced feed stream into a magnetic        product stream and a non-magnetic feed stream;    -   iii) optionally isolating a ferrous product from the magnetic        product stream;    -   iv) stripping the non-magnetic feed stream with a stripping        solvent to form a stripped slurry stream;    -   v) separating the stripped slurry stream into an oversize solids        portion and an undersize stripped slurry stream;    -   vi) optionally separating the oversize solids portion of the        stripped slurry stream into a preliminary aluminum product        stream, a preliminary copper product stream, and a plastic        product stream;    -   vii) subjecting the undersize stripped slurry stream to a        solid-liquid separation to form a black mass solid stream and        recovered stripping solvent;    -   viii) leaching the black mass solid stream with an acid to form        a pregnant leach solution and residual solids;    -   ix) separating the pregnant leach solution from the residual        solids to form a first product stream comprising the residual        solids and a second product stream comprising the pregnant leach        solution;    -   x) optionally isolating a graphite product from the first        product stream;    -   xi) isolating a copper product from the second product stream to        form a third product stream;    -   xii) isolating an aluminum (Al) and/or iron (Fe) product from        the third product stream to form a fourth product stream;    -   xiii) isolating a cobalt (Co), nickel (Ni), and/or manganese        (Mn) product from the fourth product stream to form a fifth        product stream;    -   xiv) isolating a salt by-product from the fifth product stream        to form a sixth product stream; and    -   xv) isolating a lithium product from the sixth product stream.

In another aspect, there is provided an apparatus for carrying out sizereduction of battery materials under immersion conditions, comprising:

a housing configured to hold an immersion liquid;

a first feed chute defining an opening therein for receiving batterymaterials of a first type into the housing;

a first submergible comminuting device disposed within the housing toreceive the battery materials of the first type from the first feedchute, wherein said first submergible comminuting device is configuredto cause a size reduction of the battery materials of the first type toform a first reduced-size battery material; and

a second submergible comminuting device disposed within the housing toreceive the first reduced-size battery material from the firstsubmergible comminuting device, wherein the second submergiblecomminuting device is configured to cause a further size reduction inthe first reduced-size battery material to form a second reduced-sizebattery material.

In yet another aspect, there is provided a system for carrying out sizereduction of battery materials under immersion conditions, comprising:

(a) a first submergible comminuting device to receive battery materialsof a first type, wherein the first submergible comminuting device causesa size reduction in the battery materials of the first type to form afirst reduced-size battery material;

(b) a second submergible comminuting device to receive the firstreduced-size battery material, wherein the second submergiblecomminuting device causes a further size reduction in the firstreduced-size battery material to form a second reduced-size batterymaterial; and

(c) an immersion liquid in which each of the first submergiblecomminuting device, the second submergible comminuting device, the firstreduced-size battery material, and the second reduced-size batterymaterial are submerged.

BRIEF DESCRIPTION OF THE FIGURES

For a better understanding of the present application, as well as otheraspects, embodiments, and further features thereof, reference is made tothe following description which is to be used in conjunction with theaccompanying figures and/or tables, where:

FIG. 1A depicts a block flow diagram of an embodiment of a first processas described herein (“Process 1”).

FIG. 1B depicts a block flow diagram of an embodiment of a secondprocess as described herein (“Process 2”).

FIG. 2 depicts an exemplary apparatus and system in accordance with anembodiment of the present application.

FIG. 3(a) is a picture of the modified Franklin-Miller Taskmaster TM8500Shredder™ which is a dual-shaft shredder that has been modified tooperate under immersion conditions.

FIG. 3(b) is a picture of the control and electrical panel for themodified Franklin-Miller Taskmaster TM8500 Shredder™ shown in FIG. 3(a).

FIG. 3(c) is a picture of the comminuting portion of the modifiedFranklin-Miller Taskmaster TM8500 Shredder™ shown in FIG. 3(a).

FIG. 3(d) is a picture of the comminuting portion of the modifiedFranklin-Miller Taskmaster TM8500 Shredder™ shown in FIG. 3(a) showingthe comminuting portion immersed in the immersion liquid.

FIG. 4(a) is a picture of material after passing through 1st stage wetshredding (Physical Validation Example; Coarse Shredder mini-piloting).

FIG. 4(b) is a picture of material after passing through 2nd stage wetshredding (Physical Validation Example; Fine Shredder mini-piloting).

FIG. 4(c) is a picture of material after passing through granulator(Physical Validation Example; Dry Shredder mini-piloting).

FIG. 4(d) is a picture of fine particle material isolated following1^(st) stage wet shredding after passing through a wire mesh screen with500 μm openings and subsequent filtration.

Table 1 delineates a potential summary forecast of spent/discarded smalland large format Li-ion battery components in 2025 and 2030;

Table 2 delineates example design and IDEAS process simulationparameters for Phase 1 feed size reduction steps of each of Processes 1and 2;

Table 3 delineates example design and IDEAS process simulationparameters for Phase 2 magnetic separation and eddy current separationof Process 1;

Table 4 delineates example design and IDEAS process simulationparameters for Phase 2 leaching and countercurrent decantation (CCD)steps of Process 1;

Table 5 delineates key reaction chemistry for Phase 2 leaching step ofProcess 1 and Process 2 per the IDEAS process simulation parameters;

Table 6 delineates example design and IDEAS process simulationparameters for Phase 2 intermediate product preparation steps of Process1;

Table 7 delineates example design and IDEAS process simulationparameters for Phase 3 final product preparation steps of Process 1; and

Table 8 delineates key reaction chemistry for Phase 3 final productpreparation steps, per the IDEAS process simulation parameters ofProcess 1.

Table 9 delineates example design and IDEAS process simulationparameters for Phase 2 magnetic separation, stripping, and optionaldensimetric separation of Process 2;

Table 10 delineates example design and IDEAS process simulationparameters for Phase 2 leaching of Process 2;

Table 11 delineates example design and IDEAS process simulationparameters for Phase 2 intermediate product preparation steps of Process2;

Table 12 delineates example design and IDEAS process simulationparameters for Phase 3 final product preparation steps of Process 2; and

Table 13 delineates key reaction chemistry for Phase 3 final productpreparation steps of Process 2, per the IDEAS process simulationparameters.

Table 14 delineates the mechanical design criteria for an embodiment ofan apparatus/system for carrying out size reduction of battery materialsunder immersion conditions.

DETAILED DESCRIPTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this application belongs.

As used in the specification and claims, the singular forms “a”, “an”and “the” include plural references unless the context clearly dictatesotherwise.

The term “comprising” as used herein will be understood to mean that thelist following is non-exhaustive and may or may not include any otheradditional suitable items, for example one or more further feature(s),component(s) and/or ingredient(s) as appropriate.

The term “battery” or “batteries” are used herein refer to rechargeablelithium-ion batteries, unless the context clearly dictates otherwise.

Lithium-Ion Batteries

Components

Lithium-ion batteries are a type of rechargeable battery in whichlithium ions drive an electrochemical reaction. Lithium has a highelectrochemical potential and provides a high energy density for weight.Typically, lithium-ion battery cells have four key components:

-   -   a. Positive electrode/cathode: comprises differing formulations        of lithium metal oxides and lithium iron phosphate depending on        battery application and manufacturer, intercalated on a cathode        backing foil/current collector (e.g. aluminum)—for example:        LiNi_(x)Mn_(y)Co_(z)O₂ (NMC); LiCoO₂ (LCO); LiFePO₄ (LFP);        LiMn₂O₄ (LMO); LiNi_(0.8)Co_(0.15)Al_(0.05)O₂ (NCA);    -   b. Negative electrode/anode: generally, comprises graphite        intercalated on an anode backing foil/current collector (e.g.        copper);    -   c. Electrolyte: for example, lithium hexafluorophosphate        (LiPF₆), lithium tetrafluoroborate (LiBF₄), lithium perchlorate        (LiClO₄), lithium hexafluoroarsenate monohydrate (LiAsF₆),        lithium trifluoromethanesulfonate (LiCF₃SO₃), lithium        bis(bistrifluoromethanesulphonyl) (LiTFSI), lithium        organoborates, or lithium fluoroalkylphosphates dissolved in an        organic solvent (e.g., mixtures of alkyl carbonates, e.g. C₁-C₆        alkyl carbonates such as ethylene carbonate (EC, generally        required as part of the mixture for sufficient negative        electrode/anode passivation), ethyl methyl carbonate (EMC),        dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene        carbonate (PC)); and    -   d. Separator between the cathode and anode: for example, polymer        or ceramic based.

Thus, rechargeable lithium-ion batteries comprise a number of differentmaterials. The term “black mass” refers to the combination of cathodeand/or anode electrode powders comprising lithium metal oxides andlithium iron phosphate (cathode) and graphite (anode), as referencedabove. Materials present in rechargeable lithium-ion batteries thereforeinclude organics such as alkyl carbonates (e.g. C₁-C₆ alkyl carbonates,such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethylcarbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), andmixtures thereof), iron, aluminum, copper, plastics, graphite, cobalt,nickel, manganese, and of course lithium. Recovering such materials fromrechargeable lithium-ion batteries is highly desirable.

Lithium-ion battery cells are manufactured in a variety of shapes/formfactors, such as:

-   -   a. cylindrical cells,    -   b. prismatic cells; and    -   c. pouch cells.

Small format lithium-ion batteries (e.g. in consumer electronicapplications) generally consist of one to several cells, each cellhaving a cathode, anode, electrolyte, and a separator. Typically, eachcell is housed in steel, aluminum, and/or plastic. If the small formatlithium-ion battery includes multiple cells (e.g. as generally the casein laptop lithium-ion batteries), the overall battery pack is typicallyhoused in plastic, or possibly other materials depending on theapplication, such as aluminum and/or steel.

Large format lithium-ion battery packs (e.g. in automotive andstationary energy storage system applications) are generally structuredas follows:

-   -   a. Cells: cells contain the cathode, anode, electrolyte,        separator, housed in steel, aluminum, and/or plastic;    -   b. Modules: multiple cells make up a module, typically housed in        steel, aluminum, and/or plastic; and    -   c. Battery pack: multiple modules make up a battery pack,        typically housed in steel, aluminum, and/or plastic.

An estimated weighted-average composition of mixed format lithium-ionbattery packs (i.e. weighted-average mixture of small and large formatlithium-ion batteries, incorporating contributions of specificlithium-ion battery cathode chemistries based on possible current andnear-term manufacturing) by weight percentage (i.e. kg material/kglithium-ion battery pack) comprises approximately: 4% Ni, 5% Mn, 7% Co,7% Li₂CO₃ (expressed as lithium carbonate equivalent), 10% Cu, 15% Al,16% graphite, and 33% other materials. By way of further example, anestimated possible summary of small and large format lithium-ion batterycomponents forecasted in 2025 and 2030 is provided in Table 1.

Of these components, it is estimated that approximately seven comprise≥90% of the residual value in a spent lithium-ion battery: cobalt,lithium, copper, graphite, nickel, aluminum, and manganese. For example,an estimated weighted-average composition of mixed format lithium-ionbattery packs based on residual values of contained materials in a spentlithium-ion battery (USD per kg material/kg lithium-ion battery pack)comprises approximately: 9% Ni, 2% Mn, 39% Co, 16% Li₂CO₃ (expressed aslithium carbonate equivalent) 12% Cu, 5% Al, 10% graphite, and 7% othermaterials.

Recharging

As a lithium-ion battery cell charges and discharges, lithium ions movein and out of the anode and cathode. During this electrochemicalreaction, a lithiated anode (e.g. graphite with lithium inside) and atransition metal oxide missing lithium are formed. Both the lithiatedanode and transition metal oxide are reactive. These transitionmaterials can experience ‘parasitic reactions’ with the typicallyorganic-based electrolyte solution (which as noted above contains alkylcarbonates).

The anode particularly experiences such parasitic reactions, whichresults in a solid product that deposits on the anode surface. Thissolid product is called a solid electrolyte interphase (SEI). Over time,this forms a passivating film that slows down and limits furtherelectrochemical reactions.

For example, scanning electron microscope images of aged/cycled cathodeand anode materials have shown that, with respect to cathodes oflithium-ion cells utilizing a mixed organic based electrolyte solution,the cathodes exhibit limited surface deposition of solid electrolyteinterphase. By contrast, an aged/cycled anode consisting of graphiteexhibits solid electrolyte interphase. The presence of a solidelectrolyte interphase across a layered graphite anode reduces theelectrochemical reaction efficiency that powers lithium-ion cells bylimiting sites for lithium to intercalate. Over time, this reduces thelithium-ion battery cell's ability to deliver energy and eventuallycauses the battery cell to become ‘spent’.

Process 1

In one embodiment of Process 1, there is provided a process forrecovering materials from rechargeable lithium-ion batteries comprising:

-   -   a) processing lithium-ion batteries to form a size-reduced feed        stream;    -   b) separating the size-reduced feed stream into a magnetic        product stream and a first non-magnetic feed stream;    -   c) optionally isolating a ferrous product from the magnetic        product stream;    -   d) separating the first non-magnetic feed stream into an        aluminum product stream and a second non-magnetic feed stream;    -   e) optionally isolating an aluminum product from the aluminum        product stream;    -   f) leaching the second non-magnetic feed stream with acid to        form a leached slurry;    -   g) separating the leached slurry into a first product stream and        a second product stream;    -   h) optionally isolating a first copper product from the first        product stream;    -   i) separating the second product stream into a graphite product        stream and a third product stream;    -   j) optionally isolating a graphite product from the graphite        product stream;    -   k) optionally filtering the third product stream to isolate        organics and solids to form a fourth product stream;    -   l) depositing a second copper product from the third or fourth        product stream to form a fifth product stream;    -   m) isolating a Co, Ni, and/or Mn product from the fifth product        stream to form a sixth product stream; and    -   n) isolating a lithium product from the sixth product stream.

For example, see FIG. 1A, which depicts a block flow diagram of anembodiment of Process 1.

In another embodiment of Process 1, processing step a) comprises:optionally discharging lithium-ion batteries to approximately between1-2V; or, alternatively, to approximately 0V; optionally storingdischarged energy in a power bank; crushing, shredding, or milling thelithium-ion batteries under aqueous immersion; optionally separating thecrushed, shredded, or milled lithium-ion batteries into a firstreduced-sized feed stream having feed material of a first size, and asecond reduced-sized feed stream having feed material of a second size;and optionally crushed, shredded, or milled the second reduced-sizedfeed stream to have feed material of the first size. In anotherembodiment, aqueous immersion comprises water or brine immersion. In yetanother embodiment, the first size is approximately ≤10 mm. In still yetanother embodiment, processing step a) has an operating temperature ofapproximately ≥2° C.-<100° C.; or alternatively, approximately ≥2°C.-≤69° C.; or, alternatively, approximately 60° C. In still yet anotherembodiment separating step b) comprises: separating the size-reducedfeed stream into the magnetic product stream and the first non-magneticfeed stream via wet magnetic separation. In another embodiment,separation step d) comprises: separating the aluminum product stream andthe second non-magnetic feed stream from the first non-magnetic feedstream via eddy current separation, densimetric separation, air-sortingseparation, or a combination thereof. In still yet another embodiment,the acid of leaching step f) comprises sulfuric acid, a mixture ofsulfuric acid and hydrogen peroxide, nitric acid, a mixture of nitricacid and hydrogen peroxide, or hydrochloric acid. In still yet anotherembodiment, separating step g) comprises: separating the leached slurryinto the first product stream and the second product stream viacountercurrent decantation. In another embodiment, separating step i)comprises separating the second product stream into a graphite productstream and a third product stream via: agglomeration optionally using aflocculant; and flotation. In another embodiment, flotation involves afirst flotation step and a second flotation step. In yet anotherembodiment, filtering step k) comprises: filtering the third productstream to isolate organics and solids via dual media filtration; andoptionally filtering the fourth product stream through an activatedcarbon filter. In another embodiment, dual media filtration involvesfiltering the third product stream through a dual media filter havinganthracite as a first media and garnet as a second media. In yet anotherembodiment, depositing step l) comprises: isolating a copper productstream from the third or fourth product stream, and depositing Cu⁰ fromthe copper product stream via electrowinning. In another embodiment,isolating the copper product stream from the third or fourth productstream involves copper ion exchange or copper solvent extraction. In yetanother embodiment, copper solvent extraction involves using anextractant, such as an organic ketoxime extractant. In still yet anotherembodiment, isolating step m) comprises: adding a source of hydroxide tothe fifth product stream to precipitate a Co, Ni, and/or Mn hydroxideproduct; adding a source of carbonate to the fifth product stream toprecipitate a Co, Ni, and/or Mn carbonate product; evaporativecrystallizing the fifth product stream in the presence of a sulfatesource to form a Co, Ni, and/or Mn sulfate product; or adding a sourceof hydroxide to the fifth product stream to precipitate a Co, Ni, and/orMn hydroxide product, followed by thermal dehydration to produce a Co,Ni, and/or Mn oxide product. In another embodiment, isolating step n)comprises: adding a carbonate to either the sixth product stream toprecipitate lithium carbonate; or adding a hydroxide to either the sixthproduct stream to form a lithium hydroxide solution, and evaporativecrystallizing the lithium hydroxide solution to form lithium hydroxidemonohydrate. In another embodiment, the process further comprisespurifying the lithium carbonate via: converting the lithium carbonateinto lithium bicarbonate; and steam-treating the lithium bicarbonate tore-form lithium carbonate. In another embodiment, the process furthercomprises purifying the lithium hydroxide monohydrate via: dissolvingthe lithium hydroxide monohydrate in water; and recrystallizing thelithium hydroxide monohydrate using a mechanical vapor recompressioncrystallizer. In yet another embodiment, when the acid of leaching stepf) comprises sulfuric acid, or a mixture of sulfuric acid and hydrogenperoxide, the process further comprises: step (o) of isolating a sulfateproduct stream from either the fifth or sixth product stream. In anotherembodiment, isolating step o) comprises: evaporative crystallizing thesulfate product stream to form a sulfate product; or crystallizing thesulfate product stream using draft tube baffle crystallizers to form asulfate product.

Thus, in an embodiment of Process 1 of the present application, there isprovided a process for recovering materials from rechargeablelithium-ion batteries comprising three main phases: (i) feed sizereduction (e.g., see FIG. 1A, step a); (ii) leaching, countercurrentdecantation, and intermediate product preparation (e.g., see FIG. 1A,steps b-f); and (iii) final product preparation (e.g., see FIG. 1A,steps g-n).

Referring to FIG. 1A, step a) provides a size-reduced feed stream thatresults from feed size reduction.

In an embodiment of feed size reduction, there is provided a processcomprising optionally discharging small format lithium-ion batteries(e.g., from phones, laptops, etc.) and/or large format lithium-ionbatteries (e.g. from electric vehicles) to approximately between 1-2V;or, alternatively to approximately 0V. In another embodiment, there isprovided a process comprising optionally storing discharged energy in acentral power bank (e.g. to provide peak-load reduction for plantfacility-wide power consumption).

In another embodiment of feed size reduction, there is provided aprocess comprising crushing, shredding, or milling the optionallydischarged lithium-ion batteries to form a reduced-sized battery feedstream. In embodiments, the batteries are crushed/shredded to a size of≤10 mm. In further embodiments, the batteries are crushed/shredded underwater/aqueous solution immersion; or, more particularly, under water orbrine immersion (to absorb heat from sparking, etc.). In yet otherembodiments, the batteries are crushed/shredded at a temperature betweenapproximately ≥2° C.-<100° C.; or alternatively, approximately ≥2°C.-≤69° C.; or, alternatively, approximately 60° C.

In another embodiment of feed size reduction, there is provided aprocess comprising a two stage-crushing of the batteries to form areduced-sized battery feed stream. In embodiments, the two-stagecrushing occurs under water/aqueous solution immersion; or, moreparticularly, under water or brine immersion to: (i) restrictaccumulation of oxygen; (ii) minimize risk of combustion during crushingby suppressing any sparking caused by crushing and absorbing it as heat;and, (iii) entrain the batteries' electrolyte solution. In someembodiments, the brine solution comprises an aqueous sodium chloridesolution. In other embodiments, the brine solution comprises a diluteaqueous solution of calcium hydroxide (also known as slaked or hydratedlime) to assist with neutralizing potential halides from electrolytesalts and thereby minimizing hydrolysis (e.g. formation of aqueoushydrofluoric acid/HF) that may result in increased materials/equipmentcorrosion; and/or, to minimize potential to form sodium fluoride salts.In embodiments, the two-stage crushing comprises a first crusher thataccepts large format lithium-ion batteries and reduces their size to≤400 mm; and, a second crusher that accepts small format lithium-ionbatteries and reduced-size large format lithium-ion batteries, andreduces that combined battery feed stream to a size of ≤100 mm. Inembodiments, the two-stage crushing occurs at a temperature betweenapproximately ≥2° C.-<100° C.; or alternatively, approximately 2°C.-≤69° C.; or, alternatively, approximately 60° C.

In another embodiment of feed size reduction, there is provided aprocess comprising screening of the reduced-sized battery feed stream.In embodiments, the reduced-sized battery feed stream is separated intoan undersized fraction of ≤10 mm and an oversized fraction of ≥10 mm to≤100 mm. In embodiments, the undersized fraction undergoes solid-liquidseparation to form a filter cake comprising particles that are ≤10 mm.In some embodiments, the solid-liquid separation occurs via a beltfilter. In embodiments, the oversized fraction is shredded to ≤10 mm. Insome embodiments, the oversized fraction is shredded using shredderssimilar to industrial scale shredders found in waste electronicrecycling and food processing facilities. In embodiments, the undersizedfraction of ≤10 mm and oversized fraction is shredded to ≤10 mm iscombined to form a size-reduced feed stream, as per FIG. 1A, step a.

In another embodiment of feed size reduction, there is provided aprocess comprising magnetic separation (for example, see FIG. 1A, stepb)) of the size-reduced battery feed to separate magnetic/ferrousmaterials (e.g. steel sheet; ferrous product(s); magnetic productstream, FIG. 1A) from non-magnetic/non-ferrous and inert materials(e.g., 1^(st) non-magnetic feed stream, FIG. 1A). In embodiments, themagnetic separation is wet magnetic separation. In some embodiments, thewet magnetic separation comprises ‘rougher’ and ‘cleaner’ magneticseparation steps. In some embodiments, the wet magnetic separation useslow intensity magnetic separation equipment.

In another embodiment of feed size reduction, there is provided aprocess comprising eddy current separation of thenon-magnetic/non-ferrous size-reduced battery feed to separate anyresidual magnetic/ferrous materials (e.g. steel sheet; ferrousproduct(s)) from the non-magnetic/non-ferrous and inert material. Inembodiments, the eddy current separation provides for separation of analuminum product stream (for example, see FIG. 1A, step d) and aluminumproduct stream). In other embodiments, eddy current separation,densimetric separation, air-sorting separation, or a combination thereofprovide for separation of the aluminum product stream. In embodiments,the eddy current separation provides for isolation of any residualmagnetic/ferrous materials (e.g. steel sheet; ferrous product(s)) torecycle back to the wet magnetic separation.

In an embodiment of leaching, countercurrent decantation, andintermediate product preparation, there is provided a process comprisingacid leaching of the non-magnetic/non-ferrous and inert materials fromeddy current separation (excluding separated aluminum product stream;for example, the 2^(nd) non-magnetic feed stream, FIG. 1A) to form aleached slurry (for example, see FIG. 1A, step f)). In embodiments, theacid used is sulfuric acid, hydrochloric acid, or nitric acid. In someembodiments, hydrogen peroxide is used to facilitate leaching of noblermetals. In some embodiments, leaching occurs at an operating temperaturebetween approximately 60-95° C. In some embodiments, leaching occurs ina conical-bottom tank under high shear agitation.

In an embodiment of leaching, countercurrent decantation, andintermediate product preparation, there is provided a process comprisingscreening the leached slurry into an undersized fraction of ≤5 mm and anoversized fraction of ≥5 mm. In embodiments, the oversized fraction isrecycled back to the wet magnetic separation for further separation.

In an embodiment of leaching, countercurrent decantation, andintermediate product preparation, there is provided a process comprisingcountercurrent decantation (CCD) of the leached slurry (for example, seeFIG. 1A, step g)). In embodiments, CCD separates slimes/residue or‘copper concentrate’, consisting predominantly of copper, some residualshredded aluminum, residual shredded steel, paper and plastic, as anunderflow stream (e.g., 1^(st) product stream, FIG. 1A); and, separatesa combined aqueous leachate phase (pregnant leach solution or PLS) andfloating/low density phase (e.g., graphite, organic) as an overflowstream (e.g., 2^(nd) product stream, FIG. 1A). In some embodiments, theCCD uses several stages of high density thickeners.

In an embodiment of leaching, countercurrent decantation, andintermediate product preparation, there is provided a process whereinthe CCD overflow stream from reports to an agglomeration tank, in whicha flocculant is added to assist in agglomeration of the graphite andorganic phases. In embodiments, the solution from the agglomeration tankreports to flotation cells to selectively separate a hydrophobic phase(e.g., graphite agglomerated with flocculant, and organic; graphiteproduct stream, FIG. 1A) from a hydrophilic phase (e.g., aqueous PLS).In embodiments, the flotation cells include a ‘rougher flotation cell’that completes a preliminary separation of the hydrophobic andhydrophilic phases; and, a ‘cleaner flotation cell’ to which the‘rougher flotation cell’ froth reports to, to further separate thehydrophobic and hydrophilic phases. In embodiments, froth from the‘cleaner flotation cell’ reports to solid-liquid separation tooptionally isolate a solid or ‘graphite concentrate’ phase (for example,see FIG. 1A, step j)). In some embodiments, a centrifuge is used toachieve solid-liquid separation.

In an embodiment of leaching, countercurrent decantation, andintermediate product preparation, there is provided a process comprisingcombining residual PLS from the ‘rougher flotation cell’ and ‘cleanerflotation cell’ (e.g., 3^(rd) product stream, FIG. 1A) (optionally withliquid (e.g. centrate) from the solid-liquid filtration of froth fromthe ‘cleaner flotation cell’; step j), FIG. 1A); and, optionallyfiltering the combined liquid stream through a dual media filter toseparate entrained organics (for example, see FIG. 1A, step k)). Inembodiments, a dual media filter similar to filters found in coppersolvent extraction is used. In embodiments, the dual media filtercomprises filtration media such as anthracite, garnet, and/or sand. Insome embodiments, the liquid stream output from the dual media filter(e.g., 4^(th) product stream, FIG. 1A) optionally reports to anactivated carbon filter to further separate any entrained organics.

In an embodiment, there is provided a process optionally comprisingdewatering the magnetic/ferrous materials (e.g., steel sheet; ferrousproduct(s)) from magnetic separation; and, collecting and storing saiddewatered materials (for example, see FIG. 1A, step c) and ferrousproduct). In embodiments, the process optionally comprises dewateringthe aluminum product stream from eddy current separation; and,collecting and storing the dewatered aluminum product (for example, seeFIG. 1A, step e) and aluminum product). In embodiments, a dewateringscreen is used, wherein the screen is steeply inclined to facilitatewater/aqueous solution drainage.

In an embodiment of final product preparation, there is provided aprocess optionally comprising a solid-liquid separation ofslimes/residue or final underflow stream from the CCD to produce acopper concentrate. In some embodiments, a belt filter is used toachieve solid-liquid separation. For example, see FIG. 1A, step h) and1^(st) copper product.

In an embodiment of final product preparation, there is provided aprocess optionally comprising collecting graphite concentrate from thesolid-liquid separation of froth from the ‘cleaner flotation cell’. Insome embodiments, the graphite concentrate is collected as the solidproduct from centrifugation of froth from the ‘cleaner flotation cell’.For example, see FIG. 1A, step j) and graphite product.

In an embodiment of final product preparation, there is provided aprocess comprising a copper-ion exchange of the liquid stream outputfrom dual media filtration. In embodiments, a copper selective resin isused; for example, LEWATIT® M+ TP 207. In some embodiments, the processcomprises a solvent extraction of the liquid stream output from dualmedia filtration. In some embodiments, the solvent extraction involvesmixer-settler extraction stage(s) that load copper cations into a copperselective extractant, such as an organic ketoxime extractant (e.g., LIX®84) in a diluent (e.g. kerosene)). In other embodiments, the solventextraction involves mixer-settler strip stage(s) where spent electrolytefrom copper electrowinning (below) is used to strip copper-loadedorganics and transfer copper cations into an aqueous phase prior tocopper electrowinning.

In an embodiment of final product preparation, there is provided aprocess comprising copper electrowinning of a copper-rich liquor fromcopper-ion exchange to produce elemental copper (i.e., Cu⁰). Inembodiments, copper electrowinning (e.g. conventional copperelectrowinning, Emew® electrowinning, etc.) is used for deposition ofcopper/Cu⁰ as copper plate. For example, see FIG. 1A, step l) and 2^(nd)copper product.

In an embodiment of final product preparation, there is provided aprocess comprising producing a Co, Ni, and/or Mn product. Inembodiments, the Co, Ni, and/or Mn product is a hydroxide product. Inembodiments, a copper-stripped liquor from copper-ion exchange (e.g.,5^(th) product stream, FIG. 1A) is reacted with a source of hydroxide(e.g., alkali metal hydroxides such as sodium hydroxide/NaOH, alkaliearth metal hydroxides, etc.) to precipitate a Co, Ni, and/or Mnhydroxide product (for example, see FIG. 1A, Co, Ni, and/or Mn product).In other embodiments, the Co, Ni, and/or Mn product is a carbonateproduct. In embodiments, the copper-stripped liquor reporting fromcopper-ion exchange (e.g., 5^(th) product stream, FIG. 1A) is reactedwith a source of carbonate (e.g., alkali metal carbonates such as sodiumcarbonate/Na₂CO₃, alkali earth metal carbonates, etc.) to precipitate aCo, Ni, and/or Mn carbonate product (for example, see FIG. 1A, Co, Ni,and/or Mn product). In other embodiments, the Co, Ni, and/or Mn productis an oxide product. In embodiments, the copper-stripped liquor fromcopper-ion exchange (e.g., 5^(th) product stream, FIG. 1A) is reactedwith a source of hydroxide (e.g., alkali metal hydroxides such as sodiumhydroxide/NaOH, alkali earth metal hydroxides, etc.) to precipitate aCo, Ni, and/or Mn hydroxide product that reports to thermal dehydrationto produce a Co Ni, and/or Mn oxide product (e.g., cobalt (II, III)oxide, Co₃O₄, nickel (II) oxide, NiO, manganese (IV) dioxide, MnO₂; forexample, see FIG. 1A, Co, Ni, and/or Mn product). In embodiments, theCo, Ni, and/or Mn product reports to solid-liquid filtration to collecta solid filter cake. In some embodiments, a filter press is used toachieve solid-liquid separation. In other embodiments, wherein sulfuricacid or a mixture of sulfuric acid and hydrogen peroxide is used foracid leaching, the copper-stripped liquor from copper ion exchangereports to an evaporative crystallizer to produce a cobalt sulfateheptahydrate/CoSO₄.7H₂O, nickel sulfate hexahydrate/NiSO₄.6H₂O, and/ormanganese sulfate monohydrate/MnSO₄.H₂O product. In embodiments, theresulting crystallized product(s) reports to solid-liquid separation;and, separated solid product(s) reports to a drier to drive off excesswater and produce a hydrated cobalt, nickel, and/or manganese sulfate(for example, see FIG. 1A, Co, Ni, and/or Mn product). In someembodiments, a centrifuge is used to achieve solid-liquid separation.

In an embodiment of final product preparation, there is provided aprocess comprising precipitating a lithium product. In embodiments, aliquid stream output from the Co, Ni, and/or Mn product production(e.g., 6th product stream, FIG. 1A) is reacted with a carbonate, such assodium carbonate to precipitate crude lithium carbonate. In embodiments,the crude lithium carbonate product undergoes solid-liquid separation,for example using a centrifuge, and a solid cake is collected (forexample, see FIG. 1A, step n) and lithium product). In embodiments, thecrude lithium carbonate cake reports to a bicarbonation circuit forfurther purification, wherein carbon dioxide is bubbled into a tank toconvert the lithium carbonate into more soluble lithium bicarbonate(i.e. lithium carbonate ‘digestion’). In some embodiments, the liquidstream containing soluble lithium bicarbonate reports to an ion exchangeunit to selectively remove trace impurities such as calcium andmagnesium. In embodiments, the solution containing soluble lithiumbicarbonate reports to a tank where steam is bubbled through tocrystallize higher purity lithium carbonate as a solid. In otherembodiments, crystallizing the higher purity lithium carbonate compriseselectrolysis, direct immersion electric heating, element electricheating, or indirect electric heating. In some embodiments, output fromthe lithium carbonate crystallization undergoes solid-liquid separation,for example using a centrifuge, to isolate the solid lithium carbonateproduct. In other embodiments, the liquid filtrate (e.g. centrate) isrecycled to the lithium carbonate ‘digestion’ tank. In furtherembodiments, the isolated high purity solid lithium carbonate stream isdried and micronized.

In an embodiment of final product preparation, wherein sulfuric acid ora mixture of sulfuric acid and hydrogen peroxide is used for acidleaching, there is provided a process comprising crystallizing sodiumsulfate. In embodiments, filtrate (e.g. centrate) from the crude lithiumcarbonate solid-liquid separation (e.g. centrifugation) reports to anevaporative crystallizer to produce sodium sulfatedecahydrate/Na₂SO₄.10H₂O. In some embodiments, sulfuric acid is addedduring crystallization to convert residual carbonate (e.g.Na₂CO_(3(aq))) into a sulfate form. In some embodiments, the resultingcrystallized slurry reports to solid-liquid separation; and, separatedsolid product reports to a drier, wherein the drier drives off water andproduces anhydrous sodium sulfate/Na₂SO₄. In some embodiments,solid-liquid separation achieved using a centrifuge.

In an embodiment of final product preparation, wherein hydrochloric acidis used for acid leaching, there is provided a process wherein a sodiumchloride solution is produced as a by-product. In embodiments, thesodium chloride solution is: (i) recycled to the feed size reductionstep(s) for use as a brine solution, a portion of which is optionallybled to a water treatment plant followed by reuse in the facility; or(ii) crystallized to from a solid sodium chloride product, optionallyfollowed by solid-liquid separation and drying.

In an embodiment of final product preparation, wherein nitric acid or amixture of nitric acid and hydrogen peroxide is used for acid leaching,there is provided a process wherein a sodium nitrate solution isproduced as a by-product. In embodiments, the sodium nitrate solutionis: (i) crystallized to from a solid sodium nitrate product, optionallyfollowed by solid-liquid separation and drying.

Process 2

As noted above, rechargeable lithium-ion batteries comprise a number ofdifferent materials, including organics such as alkyl carbonates (e.g.C₁-C₆ alkyl carbonates), iron, aluminum, copper, plastics, graphite,cobalt, nickel, manganese, and of course lithium. In an embodiment ofProcess 2, there is provided a process for recovering materials fromrechargeable lithium-ion batteries comprising:

-   -   i) processing lithium-ion batteries to form a size-reduced feed        stream;    -   ii) separating the size-reduced feed stream into a magnetic        product stream and a non-magnetic feed stream;    -   iii) optionally isolating a ferrous product from the magnetic        product stream;    -   iv) stripping the non-magnetic feed stream with a stripping        solvent to form a stripped slurry stream;    -   v) separating the stripped slurry stream into an oversize solids        portion and an undersize stripped slurry stream;    -   vi) optionally separating the oversize solids portion of the        stripped slurry stream into a preliminary aluminum product        stream, a preliminary copper product stream, and a plastic        product stream;    -   vii) subjecting the undersize stripped slurry stream to a        solid-liquid separation to form a black mass solid stream and        recovered stripping solvent;    -   viii) leaching the black mass solid stream with an acid to form        a pregnant leach solution and residual solids;    -   ix) separating the pregnant leach solution from the residual        solids to form a first product stream comprising the residual        solids and a second product stream comprising the pregnant leach        solution;    -   x) optionally isolating a graphite product from the first        product stream;    -   xi) isolating a copper product from the second product stream to        form a third product stream;    -   xii) isolating an aluminum (Al) and/or iron (Fe) product from        the third product stream to form a fourth product stream;    -   xiii) isolating a cobalt (Co), nickel (Ni), and/or manganese        (Mn) product from the fourth product stream to form a fifth        product stream;    -   xiv) isolating a salt by-product from the fifth product stream        to form a sixth product stream; and    -   xv) isolating a lithium product from the sixth product stream.

See, for example, FIG. 1B, which depicts a block flow diagram of anembodiment of Process 2.

Thus, in an embodiment of Process 2 of the present application, there isprovided a process for recovering materials from rechargeablelithium-ion batteries comprising three main phases: (i) feed sizereduction (e.g., see FIG. 1B, steps (i) and (i)(a)); (ii) leaching, andintermediate product preparation (e.g., see FIG. 1B, steps (ii)-(x));and (iii) final product preparation (e.g., see FIG. 1B, steps(xi)-(xv)).

Referring to FIG. 1B, step i) provides a size-reduced feed stream thatresults from feed size reduction. In an embodiment of Process 2,processing step i) comprises: optionally discharging lithium-ionbatteries to approximately between 1-2V; or, alternatively, toapproximately 0V; optionally storing discharged energy in a power bank;crushing, shredding, or milling the lithium-ion batteries under aqueousimmersion; optionally separating the crushed, shredded, or milledlithium-ion batteries into a first reduced-sized feed stream having feedmaterial of a first selected size, and a second reduced-sized feedstream having feed material of a second size; and optionally crushing,shredding, or milling the second reduced-sized feed stream to have feedmaterial of the first selected size.

In another embodiment of Process 2, aqueous immersion comprisesimmersion in water, or immersion in an aqueous solution comprising (i) asalt and/or (ii) calcium hydroxide. In another embodiment, the salt isselected from an alkali metal chloride (e.g. sodium chloride (NaCl)), analkaline earth metal chloride (e.g. calcium chloride (CaCl₂)), ormixtures thereof. In yet another embodiment, the first selected size isapproximately 40 mm, preferably 10 mm. In still yet another embodiment,processing step i) has an operating temperature of approximately 2° C.to <100° C.; or alternatively, approximately 2° C. to 69° C.; or,alternatively, approximately 60° C.

Thus, in an embodiment of feed size reduction, there is provided aprocess comprising optionally discharging small format lithium-ionbatteries (e.g., from phones, laptops, etc.) and/or large formatlithium-ion batteries (e.g. from electric vehicles) to approximatelybetween 1-2V; or, alternatively to approximately 0V. In anotherembodiment, there is provided a process comprising optionally storingdischarged energy in a central power bank (e.g. to provide peak-loadreduction for plant facility-wide power consumption).

In another embodiment of feed size reduction, there is provided aprocess comprising crushing, shredding, or milling the optionallydischarged lithium-ion batteries to form a reduced-sized battery feedstream. In embodiments, the batteries are crushed/shredded to a size of≤40 mm, preferably ≤10 mm. In further embodiments, the batteries arecrushed/shredded under water/aqueous solution immersion; or, moreparticularly, under water or brine immersion (to absorb heat fromsparking, etc.). In yet other embodiments, the batteries arecrushed/shredded at a temperature between approximately ≥2° C. to <100°C.; or alternatively, approximately ≥2° C. to ≤69° C.; or,alternatively, approximately 60° C. In embodiments, aqueous immersioncomprises immersion in water, or immersion in an aqueous solutioncomprising (i) a salt and/or (ii) calcium hydroxide as noted above.

In another embodiment of feed size reduction, there is provided aprocess comprising a two stage-crushing/shredding of the batteries toform a reduced-sized battery feed stream. In embodiments, the two-stagecrushing/shredding occurs under water/aqueous solution immersion; or,more particularly, under water or brine immersion to: (i) restrictaccumulation of oxygen; (ii) minimize risk of combustion during crushingby suppressing any sparking caused by crushing and absorbing it as heat;and, (iii) entrain the batteries' electrolyte solution. In someembodiments, the brine solution comprises an aqueous sodium chloridesolution. In other embodiments, the brine solution comprises a diluteaqueous solution of calcium hydroxide (also known as slaked or hydratedlime) to assist with neutralizing potential halides from electrolytesalts and thereby minimizing hydrolysis (e.g. formation of aqueoushydrofluoric acid/HF) that may result in increased materials/equipmentcorrosion; and/or, to minimize potential to form sodium fluoride salts.In embodiments, the two-stage crushing/shredding comprises a firstcrusher/shredder that accepts large format lithium-ion batteries andreduces their size to ≤400 mm; and, a second crusher/shredder thataccepts small format lithium-ion batteries and reduced-size large formatlithium-ion batteries, and reduces that combined battery feed stream toa size of ≤100 mm. In embodiments, the two-stage crushing/shreddingoccurs at a temperature between approximately ≥2° C. to <100° C.; oralternatively, approximately ≥2° C. to ≤69° C.; or, alternatively,approximately 60° C.

In another embodiment of feed size reduction, there is provided aprocess comprising screening of the reduced-sized battery feed stream(following the above-noted two-stage crushing/shredding as well as anyadditional comminuting steps following same). In embodiments, thereduced-sized battery feed stream is separated into an undersizedfraction of ≤10 mm and an oversized fraction of ≥10 mm to ≤100 mm. Inembodiments, the undersized fraction undergoes solid-liquid separationto form a filter cake comprising particles that are ≤10 mm and a liquidfiltrate stream. In some embodiments, the solid-liquid separation occursvia a belt filter. In embodiments, the oversized fraction is shredded to≤10 mm. In some embodiments, the oversized fraction is shredded usingshredders similar to industrial scale shredders found in wasteelectronic recycling and food processing facilities. In embodiments, theundersized fraction of ≤10 mm and oversized fraction shredded to ≤10 mmis combined to form a size-reduced feed stream, as per FIG. 1B, step(i).

In certain embodiments, undersize materials having a particle size of,for example, less than about 5 mm, or less than about 1-2 mm, can becollected during the feed size reduction and diverted to downstreamprocess steps. For example, per FIG. 1B, undersize materials having aparticle size of, for example, less than about 5 mm, or less than about1-2 mm, can be collected from step (i) (wherein the lithium-ionbatteries are processed to produce a size-reduced feed stream) andseparated from the remainder of the size-reduced feed stream. Forexample, such undersize materials could be collected by having theoutput of a crusher/shredder contact a metal mesh having openings sizedto permit particles having a size of less than about 5 mm or less thanabout 1-2 mm to pass through and be collected. The undersize materialsform an undersize size-reduced feed stream which can be combined with,for example, a black mass solid stream (see step (vii) of FIG. 1B;described in further detail below) and these combined materials can thenbe subjected to leaching step (viii) (described in further detailbelow).

In another embodiment of feed size reduction, there is provided anoptional process of crushing, shredding, or milling the lithium-ionbatteries under aqueous immersion in an aqueous solution to produce thesize-reduced feed stream and a liquid, wherein the liquid comprises theaqueous solution and organics (such as one or more alkyl carbonates),wherein the process further comprises: carrying out a solid-liquidseparation to separate at least a portion of the liquid from the sizereduced feed stream, and subjecting the separated liquid to a separatingstep to separate the organics from the aqueous solution (for example,see FIG. 1B, step (i)(a)). In embodiments, organics (such as one or morealkyl carbonates) are separated from the aqueous components through dualmedia filtration or vacuum distillation. In some embodiments, thefiltered organics are separated into organic rich streams. In someembodiments, the separated aqueous components are recycled to thetwo-stage crushing/shredding process.

In another embodiment, separating step ii) noted above comprises:separating the size-reduced feed stream into the magnetic product streamand the non-magnetic feed stream via wet or dry magnetic separation.Thus, in one embodiment, there is provided a process comprising magneticseparation (for example, see FIG. 1B, step (ii)) of the size-reducedbattery feed to separate magnetic/ferrous materials (e.g. steel sheet;ferrous product(s); magnetic product stream, FIG. 1B) fromnon-magnetic/non-ferrous and inert materials (e.g., non-magnetic feedstream, FIG. 1B). In embodiments, the magnetic separation is wet/drymagnetic separation. In some embodiments, the wet/dry magneticseparation comprises ‘rougher’ and ‘cleaner’ magnetic separation steps.In some embodiments, the wet/dry magnetic separation uses low intensitymagnetic separation equipment.

In another embodiment, the process comprises mixing the non-magneticfeed stream with a stripping solvent (see step (iv) of FIG. 1B) to forma stripped slurry stream. It has been found that incorporation of thestripping step can enhance recovery of materials and can facilitatedownstream processing. The stripping step can be conducted attemperatures ranging from room temperature (about 20° C.) to about 120°C., preferably from about 80° C. to about 100° C. The resulting strippedslurry stream (i.e. black mass/electrode powder stream), undergoessolid-liquid separation (see step (v) in FIG. 1B) by reporting to, forexample, a wire mesh screen with, for example, openings ranging fromabout 500 μm to about 5 mm, preferably from about 500 μm to about 2 mm,producing an oversize solids portion of the stripped slurry stream (i.e.larger solids portion of the separation)—comprising aluminum, copper,and plastics—and an undersized stripped slurry stream (i.e. liquidportion of the separation containing smaller solids having the sizerange noted above, including black mass, in admixture with same).Suitable stripping solvents can include n-methyl-2-pyrrolidone (NMP),dimethylformamide (DMF), ethyl acetate (EtOAc), isopropanol (IPA),acetone, dimethyl sulfoxide (DMSO), or diethylformamide (DEF).

The undersized stripped slurry stream reports to a filter press forsolid-liquid separation (see step (vii) in FIG. 1B) to yield a liquidcontaining the stripping solvent (i.e. recovered stripping solvent) anda black mass solid stream. The separated solvent is optionally collectedinto a tank, and is optionally recycled back to the stripping tanks foruse as make-up solvent.

The oversize solids portion of the stripped slurry stream is optionallydried by reporting to, for example, a dewatering conveyor. In anotherembodiment, the process optionally further comprises separating theoversize solids portion of the stripped slurry stream (see step (vi) ofFIG. 1B), such as by densimetric separation of the oversize solidsportion of the stripped slurry stream. Thus, in one embodiment,separation step vi) comprises separating the oversize stripped slurrystream into the preliminary aluminum product stream, the preliminarycopper product stream, and the plastic product stream via densimetricseparation. A densimetric separator unit can separate the oversizesolids portion of the stripped slurry stream into three separatestreams, including a preliminary aluminum product stream, a preliminarycopper product stream, and a plastic product stream. For example, theplastic can be separated using a liquid with a specific gravity (SG) ofabout 2.5, and thereafter aluminum can be separated from the copperusing a liquid with an SG of about 2.85. The isolated streams areoptionally washed and report to a dewatering screen to collect separateand washed preliminary aluminum product, preliminary copper product, andplastic product streams.

The black mass solid stream comprises at least one of electrode (e.g.metal oxide and/or metal phosphate cathode powders, graphite anode),plastic, and some residual non-ferrous (e.g. shredded copper and/oraluminum) components. This stream reports to a leach tank for leaching,together with the undersize size-reduced feed stream from step (i) asreferenced above.

In embodiments, the leaching step comprises acid leaching of the blackmass solid stream (see step (viii) of FIG. 1B). In certain embodiments,the acid used in the leaching step is sulfuric acid, hydrochloric acid,or nitric acid, preferably sulfuric acid. In some embodiments, hydrogenperoxide is used to facilitate leaching of nobler metals. In someembodiments, leaching occurs at an operating temperature betweenapproximately 60-95° C. In embodiments, leaching occurs in a series of 3tanks. In some embodiments, leaching occurs in conical-bottom tanksunder high shear agitation. In some embodiments, oxygen gas is spargedto further oxidize the leached solution.

In another embodiment of leaching, and intermediate product preparation,there is provided a process wherein the leached slurry is filtered (forexample, by filter press or belt filter; see step (ix) of FIG. 1B) toseparate the residual solids as a 1^(st) product stream, which report toa mixing tank, from the aqueous solution (e.g., aqueous PLS), whichforms a 2^(nd) product stream. Water is added to the mixing tank alongwith the residual solids, and the pH can be adjusted to between 4-8. Inembodiments, step x) of isolating a graphite product from the firstproduct stream comprises isolating the graphite product via flotation,wherein flotation optionally comprises a first flotation step and asecond flotation step. Thus, in embodiments, the solution from themixing tank reports to flotation cells to selectively separate ahydrophobic phase (e.g., graphite, and organic; graphite product stream,FIG. 1B) from a hydrophilic phase (e.g., mixing tank water). Inembodiments, the flotation cells include a ‘rougher flotation cell’ thatcompletes a preliminary separation of the hydrophobic and hydrophilicphases; and, a ‘cleaner flotation cell’ to which the ‘rougher flotationcell’ froth reports to, to further separate the hydrophobic andhydrophilic phases. In embodiments, froth from the ‘cleaner flotationcell’ reports to solid-liquid separation to optionally isolate a solidor ‘graphite concentrate’ phase (for example, see FIG. 1B, step (x)). Insome embodiments, a centrifuge is used to achieve solid-liquidseparation.

In another embodiment of leaching, and intermediate product preparation,there is optionally provided a process comprising filtering the PLS (2^(nd) product stream) through a dual media filter and/or belt filter toseparate entrained organics (i.e. residual alkyl carbonates) andremaining solids (not shown in FIG. 1B). In embodiments, a dual mediafilter similar to filters found in copper solvent extraction is used. Insome embodiments, a dual media filter comprises filtration media such asanthracite, garnet, and/or sand. In some embodiments, the liquid streamoutput from the dual media filter optionally reports to an activatedcarbon filter to separate out entrained organics (i.e. residual alkylcarbonates).

In an embodiment, there is provided a process of optionally comprisingdewatering the magnetic/ferrous materials (e.g., steel sheet; ferrousproduct(s)) from magnetic separation; and, collecting and storing saiddewatered materials (for example, see FIG. 1B, step iii) and ferrousproduct).

In embodiments, the process optionally comprises dewatering thepreliminary aluminum product stream from densimetric separation, and,collecting and storing the dewatered aluminum product (for example, seeFIG. 1B, step (vi)(a)) and aluminum product). In embodiments, theprocess optionally comprises dewatering the preliminary copper productstream from densimetric separation, and collecting the dewateredpreliminary copper product (for example, see FIG. 1B, step (vi)(b)). Inembodiments, the process optionally comprises dewatering the plasticproduct stream from densimetric separation, and collecting the dewateredplastic product (for example, see FIG. 1B, step (vi)(c)). Inembodiments, a dewatering screen is used, wherein the screen is steeplyinclined to facilitate water/aqueous solution drainage.

In another embodiment of final product preparation, there is provided aprocess optionally comprising collecting graphite concentrate from thesolid-liquid separation of froth from the ‘cleaner flotation cell’. Insome embodiments, the graphite concentrate is collected as the solidproduct from centrifugation of froth from the ‘cleaner flotation cell’.For example, see FIG. 1B, step x) and graphite product.

In one embodiment, step xi) noted above comprises: i. isolating a copperproduct stream from the second product stream, and ii. depositing Cu⁰from the copper product stream via electrowinning. In embodiments,isolating the copper product stream from the second product streaminvolves copper ion exchange or copper solvent extraction. Thus, inanother embodiment of final product preparation, there is provided aprocess comprising a copper-ion exchange of the 2^(nd) product stream(following the optional dual media filtration, if used) to yield acopper-stripped liquor as the 3^(rd) product stream. In embodiments, acopper selective resin is used; for example, LEWATIT® M+ TP 207 orDOWEX™ M4195. In some embodiments, the process comprises a solventextraction of the 2^(nd) product stream (again, following the optionaldual media filtration, if used) to yield a copper-stripped liquor as the3^(rd) product stream. In some embodiments, the solvent extractioninvolves mixer-settler extraction stage(s) that load copper cations intoa copper selective extractant, such as an organic ketoxime extractant(e.g., LIX® 984N) in a diluent (e.g. kerosene)). In other embodiments,the solvent extraction involves mixer-settler strip stage(s) where spentelectrolyte from copper electrowinning (below) is used to stripcopper-loaded organics and transfer copper cations into an aqueous phaseprior to copper electrowinning.

In another embodiment of final product preparation, there is provided aprocess comprising copper electrowinning of a copper-rich liquor fromcopper-ion exchange to produce elemental copper (i.e., Cu⁰). In someembodiments, there is provided a process optionally comprising copperelectrowinning of a copper-rich liquor from solvent extraction. Inembodiments, copper electrowinning (e.g. conventional copperelectrowinning, Emew® electrowinning, etc.) is used for deposition ofcopper/Cu⁰ as copper plate. For example, see FIG. 1B, step XI) andcopper product.

In one embodiment, step xii) as noted above comprises isolating thealuminum (Al) and/or iron (Fe) product from the third product stream byadding a source of hydroxide to the third product stream to precipitatea Al and/or Fe hydroxide product. Thus, in another embodiment of finalproduct preparation, there is provided a process comprising producing anAl and/or Fe product from the 3^(rd) product stream (for example, FIG.1B, step (xii)) wherein, the Al and/or Fe product is a hydroxideproduct. In embodiments, a copper-stripped liquor from copper ionexchange or solvent extraction (e.g. the 3^(rd) product stream, FIG. 1B)is optionally sparged with oxygen gas and reacted with a source ofhydroxide (e.g., alkali metal hydroxides such as sodium hydroxide/NaOH,alkali earth metal hydroxides, etc.; NaOH being a preferred source ofhydroxide) at a pH of about 3 to about 5 to precipitate an Al and/or Feproduct (for example, see FIG. 1B, Al and/or Fe product), leaving an Aland/or Fe-depleted solution (Al and/or Fe product preparation filtrate)as the 4′^(th) process stream. In some embodiments, a filter press orcentrifuge is used to achieve solid-liquid separation.

In another embodiment, isolating step xiii) noted above comprises: i.adding a source of hydroxide to the fourth product stream to precipitatea Co, Ni, and/or Mn hydroxide product; ii. adding a source of carbonateto the fourth product stream to precipitate a Co, Ni, and/or Mncarbonate product; iii. evaporative crystallizing the fourth productstream in the presence of a sulfate source to form a Co, Ni, and/or Mnsulfate product; or iv. adding a source of hydroxide to the fourthproduct stream to precipitate a Co, Ni, and/or Mn hydroxide product,followed by thermal dehydration to produce a Co, Ni, and/or Mn oxideproduct.

Thus, in another embodiment of final product preparation, there isprovided a process comprising producing a Co, Ni, and/or Mn product fromthe 4th process stream. In embodiments, the Co, Ni, and/or Mn product isa hydroxide product. In embodiments, Al and/or Fe product preparationfiltrate (e.g., the 4^(th) product stream, FIG. 1B) is reacted with asource of hydroxide (e.g., alkali metal hydroxides such as sodiumhydroxide/NaOH, alkali earth metal hydroxides, etc.; NaOH being apreferred source of hydroxide) to precipitate a Co, Ni, and/or Mnhydroxide product (for example, see FIG. 1B, Co, Ni, and/or Mn product).In other embodiments, the Co, Ni, and/or Mn product is a carbonateproduct. In embodiments, the Al and/or Fe product preparation filtrate(e.g., the 4th product stream, FIG. 1B) is reacted with a source ofcarbonate (e.g., alkali metal carbonates such as sodiumcarbonate/Na₂CO₃, alkali earth metal carbonates, etc.; Na₂CO₃, being apreferred source of carbonate) to precipitate a Co, Ni, and/or Mncarbonate product (for example, see FIG. 1B, Co, Ni, and/or Mn product).In other embodiments, the Co, Ni, and/or Mn product is an oxide product.In embodiments, the Al and/or Fe product preparation filtrate (e.g., the4^(th) product stream, FIG. 1B) is reacted with a source of hydroxide(e.g., alkali metal hydroxides such as sodium hydroxide/NaOH, alkaliearth metal hydroxides, etc.) at a pH of about 8 to about 10 toprecipitate a Co, Ni, and/or Mn hydroxide product that reports tothermal dehydration to produce a Co Ni, and/or Mn oxide product (e.g.,cobalt (II, III) oxide, Co₃O₄, nickel (II) oxide, NiO, manganese (IV)dioxide, MnO₂; for example, see FIG. 1B, Co, Ni, and/or Mn product). Inembodiments, the Co, Ni, and/or Mn product reports to solid-liquidfiltration to collect a solid filter cake. In some embodiments, a filterpress is used to achieve solid-liquid separation. The Co, Ni, and/orMn-depleted liquid forms the 5^(th) product stream.

In other embodiments, sulfuric acid or a mixture of sulfuric acid andhydrogen peroxide is used for acid leaching of the solid Co, Ni, and/orMn product, following which the leachate reports to an evaporativecrystallizer or draft tube baffle crystallizer to produce a cobaltsulfate heptahydrate/CoSO₄.7H₂O, nickel sulfate hexahydrate/NiSO₄.6H₂O,and/or manganese sulfate monohydrate/MnSO₄.H₂O product. In embodiments,the resulting crystallized product(s) reports to solid-liquidseparation; and, separated solid product(s) reports to a drier to driveoff excess water and produce a hydrated cobalt, nickel, and/or manganesesulfate (for example, see FIG. 1B, Co, Ni, and/or Mn product). In someembodiments, a centrifuge or filter press is used to achievesolid-liquid separation.

As noted above, step (xiv) comprises isolating a salt by-product fromthe fifth product stream to form a sixth product stream. In oneembodiment, isolating step xiv) comprises: i. evaporativecrystallization to isolate the salt by-product; or ii. crystallizationusing draft tube baffle crystallizers to isolate the salt by-product.Those of skill in the art will recognize that salt by-products producedby way of the earlier process steps will depend at least in part on thechoice of acid for leaching step (viii) and the choice of source ofhydroxide, carbonate, etc. in steps (xii) and (xiii). Thus, when theacid of leaching step viii) comprises sulfuric acid, the salt by-productof step xiv) will comprise a sulfate salt. When the acid of leachingstep viii) comprises hydrochloric acid or nitric acid, the saltby-product of step xiv) will comprise a chloride salt or nitrate saltrespectively.

When the acid of leaching step viii) comprises sulfuric acid; and, whenstep xii) comprises isolating the aluminum (Al) and/or iron (Fe) productfrom the third product stream by adding sodium hydroxide to the thirdproduct stream to precipitate a Al and/or Fe hydroxide product, and/orstep xiii) comprises adding sodium hydroxide to the fourth productstream to precipitate a Co, Ni, and/or Mn hydroxide product or addingsodium carbonate to the fourth product stream to precipitate a Co, Ni,and/or Mn carbonate product, the salt by-product of step xiv) comprisessodium sulfate. Thus, in an embodiment of final product preparation,there is provided a process comprising crystallizing sodium sulfate fromthe 5^(th) product stream to form a sodium sulfate solid product, and asodium-depleted liquid that forms the 6^(th) product stream. Inembodiments, filtrate from the Co, Ni, and/or Mn product preparationreports to an evaporative crystallizer to produce sodium sulfatedecahydrate/Na₂SO₄.10H₂O. In some embodiments, the resultingcrystallized slurry reports to solid-liquid separation; and, separatedsolid product reports to a drier, wherein the drier drives off water andproduces anhydrous sodium sulfate/Na₂SO₄. In some embodiments,solid-liquid separation achieved using a centrifuge.

In one embodiment, isolating step xv) as noted above, relating toisolating a lithium product from the sixth product stream, comprises: i.adding a carbonate to the sixth product stream to precipitate lithiumcarbonate; or ii. adding a hydroxide to the sixth product stream to forma lithium hydroxide solution, and evaporative crystallizing the lithiumhydroxide solution to form lithium hydroxide monohydrate. In oneembodiment, the process further comprises purifying the lithiumcarbonate via: i. converting the lithium carbonate into lithiumbicarbonate; and ii. steam-treating the lithium bicarbonate to re-formlithium carbonate. In another embodiment, the process further comprisespurifying the lithium hydroxide monohydrate via: i. dissolving thelithium hydroxide monohydrate in water; and ii. recrystallizing thelithium hydroxide monohydrate using a mechanical vapor recompressioncrystallizer.

Thus, in an embodiment of final product preparation, there is provided aprocess comprising precipitating a lithium product from the 6^(th)product stream. In embodiments, a liquid stream output from the sodiumsulfate product production (e.g., 6^(th) product stream, FIG. 1B) isreacted with a carbonate, such as sodium carbonate to precipitate crudelithium carbonate. In embodiments, the crude lithium carbonate productundergoes solid-liquid separation, for example using a centrifuge, and asolid cake is collected (for example, see FIG. 1B, step (xv) and lithiumproduct). In embodiments, the crude lithium carbonate cake reports to abicarbonation circuit for further purification, wherein carbon dioxideis bubbled into a tank to convert the lithium carbonate into moresoluble lithium bicarbonate (i.e. lithium carbonate ‘digestion’). Insome embodiments, the liquid stream containing soluble lithiumbicarbonate reports to an ion exchange unit to selectively remove traceimpurities such as calcium and magnesium. In embodiments, the solutioncontaining soluble lithium bicarbonate reports to a tank where steam isbubbled through to crystallize higher purity lithium carbonate as asolid. In other embodiments, crystallizing the higher purity lithiumcarbonate comprises electrolysis, direct immersion electric heating,element electric heating, or indirect electric heating. In someembodiments, output from the lithium carbonate crystallization undergoessolid-liquid separation, for example using a centrifuge, to isolate thesolid lithium carbonate product. In other embodiments, the liquidfiltrate (e.g. centrate) is recycled to the lithium carbonate‘digestion’ tank. In further embodiments, the isolated high purity solidlithium carbonate stream is dried and micronized.

In an embodiment of final product preparation, wherein sulfuric acid ora mixture of sulfuric acid and hydrogen peroxide/oxygen is used for acidleaching, there is provided a process comprising crystallizing sodiumsulfate. In embodiments, filtrate (e.g. centrate) from the crude lithiumcarbonate solid-liquid separation (e.g. centrifugation) reports to anevaporative crystallizer to produce sodium sulfatedecahydrate/Na₂SO₄.10H₂O. In some embodiments, sulfuric acid is addedduring crystallization to convert residual carbonate (e.g.Na₂CO_(3(aq))) into a sulfate form. In some embodiments, the resultingcrystallized slurry reports to solid-liquid separation; and, separatedsolid product reports to a drier, wherein the drier drives off water andproduces anhydrous sodium sulfate/Na₂SO₄. In some embodiments,solid-liquid separation achieved using a centrifuge.

In another embodiment of final product preparation, wherein hydrochloricacid is used for acid leaching, there is provided a process wherein asodium chloride solution is produced as a by-product. In embodiments,the sodium chloride solution is: (i) recycled to the feed size reductionstep(s) for use as a brine solution, a portion of which is optionallybled to a water treatment plant followed by reuse in the facility; or(ii) crystallized to from a solid sodium chloride product, optionallyfollowed by solid-liquid separation and drying.

In another embodiment of final product preparation, wherein nitric acidor a mixture of nitric acid and hydrogen peroxide is used for acidleaching, there is provided a process wherein a sodium nitrate solutionis produced as a by-product. In embodiments, the sodium nitrate solutionis: (i) crystallized to from a solid sodium nitrate product, optionallyfollowed by solid-liquid separation and drying.

Apparatus and System

In one aspect, there is provided an apparatus for carrying out sizereduction of battery materials under immersion conditions. In oneembodiment, the apparatus comprises: a housing configured to hold animmersion liquid; a first feed chute (e.g. hopper) defining an openingtherein for receiving battery materials of a first type into thehousing; a first submergible comminuting device disposed within thehousing to receive the battery materials of the first type from thefirst feed chute, wherein said first submergible comminuting device isconfigured to cause a size reduction of the battery materials of thefirst type to form a first reduced-size battery material; and a secondsubmergible comminuting device disposed within the housing to receivethe first reduced-size battery material from the first submergiblecomminuting device, wherein the second submergible comminuting device isconfigured to cause a further size reduction in the first reduced-sizebattery material to form a second reduced-size battery material.

In these embodiments, a housing can be formed as a single piece or canbe a multi-part component, so long as the housing forms a unitarystructure that houses the submergible components of the apparatus andsystem as herein described to contain an immersion liquid in which thesubmergible components are immersed and to prevent unintended leakage ofthe immersion liquid to an external environment. The housing is formedfrom a material that is compatible with the immersion liquid (describedin further detail below), as well as with components of the batterymaterials, such as components of lithium-ion batteries as describedabove (e.g. metals, metal oxides, electrolytes, and organics (i.e. alkylcarbonates) typically found in lithium-ion batteries). In oneembodiment, the housing is formed from a metal (such as iron), a metalalloy (such as steel (e.g. carbon steel, stainless steel)), fiberglass(such as polyester resin), or plastic (such as polyethylene orpolypropylene). In one embodiment, the housing is formed from stainlesssteel, such as austenitic stainless steel (e.g. 304 stainless steel).

Those of skill in the art will appreciate that a submergible comminutingdevice refers to a device wherein at least the comminuting portion ofthe device is capable of being completely submerged in a liquid, such asan immersion liquid as described herein, whereas the remainder of thecomminuting device is rendered water-tight/sealed to prevent entry ofthe liquid into the portion of the comminuting device housing theelectronics, etc. The provision of appropriate water-tight seals aroundthe drive shaft and/or other elements of the comminuting device canrender the comminuting device submergible.

The apparatus can optionally comprise means for delivering the batterymaterials of the first type from the first feed chute to the firstsubmergible comminuting device. Alternatively, the first feed chute candeliver the battery materials of the first type directly to the firstsubmergible comminuting device and no intervening delivery means isrequired. In an embodiment where the delivery means is present, theapparatus can comprise a delivery chute extending from the first feedchute to the first submergible comminuting device, wherein gravity feedis used to deliver battery materials of the first type from the firstfeed chute to the first submergible comminuting device via the deliverychute. In another embodiment where the delivery means is present, theapparatus can comprise a submergible conveyor for delivering the batterymaterials of the first type from the first feed chute to the firstsubmergible comminuting device—the battery materials of the first typecan be fed directly onto the submergible conveyor, or a delivery chutecould be disposed between the first feed chute and the submergibleconveyor to deliver the battery materials of the first type to thesubmergible conveyor.

The apparatus also comprises means for delivering the first reduced-sizebattery material from the first submergible comminuting device to thesecond submergible comminuting device. In one embodiment, the apparatuscomprises a delivery chute extending from the output of the firstsubmergible comminuting device to the second submergible comminutingdevice, wherein gravity feed is used to deliver the first reduced-sizebattery material from the first submergible comminuting device to thesecond submergible comminuting device. In another embodiment, theapparatus further comprises a submergible conveyor for delivering thefirst reduced-size battery material from the first submergiblecomminuting device to the second submergible comminuting device, whereinthe submergible conveyor receives the first reduced-size batterymaterial from the output of the first submergible comminuting device anddelivers the first reduced-size battery material to the secondsubmergible comminuting device for further comminution.

In another embodiment, the submergible conveyor(s) is/are selected froma chain conveyor, a screw conveyer, or a belt conveyor. In yet anotherembodiment, the submergible conveyor(s) is/are a chain conveyor(s).

As is known to the skilled worker, a chain conveyor may be comprised ofa flat mesh formed by links which is looped around two powered rollers.The mesh can be selected to comprise links forming openings of anydesired size and can be formed of any standard material used to makechain conveyors, for example, a metal mesh. Use of chain conveyorsprovides particular advantages over use of other types of conveyors,including providing increased durability and/or ability to transportlarge loads of materials (volume- and weight-wise) compared to otherconveyors known in the art, such as belt or screw conveyors.

In other embodiments, the submergible conveyor(s) can be self-cleaning.A self-cleaning conveyor as referenced herein refers to a conveyor thatenables an operator to remove accumulated material without interruptingthe function of the conveyor, which can be advantageously used in thesystem and apparatus described herein.

In embodiments comprising a self-cleaning conveyor, undersized materialscan pass through, for example, a chain conveyor into a collectionelement which can be separate from or integral with other components ofthe disclosed apparatus. As with the housing, the collection element canbe constructed from any material that is compatible with the immersionliquid (described in further detail below), as well as with componentsof the battery materials, such as components of lithium-ion batteries asdescribed above (e.g. metals, metal oxides, electrolytes, and organics(i.e. alkyl carbonates) typically found in lithium-ion batteries). Inone embodiment, the collection element is formed from stainless steel,such as austenitic stainless steel (e.g. 304 stainless steel). Acollection element can comprise any suitable form dimensioned forcollecting undersized materials, for example, into a substantiallytubular, rectangular or triangular prism shape or can be a collectiontank. Collected undersized materials can fall, be drained or transportedinto a collection element configured to enable an operator to removecollected undersized materials by any suitable means known in the art,for example, via suction means such as vacuuming or alternatively viaapplying a pressure to divert the undersized materials to downstreamapparatuses/systems/processes. In one embodiment, the collection elementhas a smooth surface over which collected undersized materials canfreely flow for facilitation of removal. In another embodiment, a pipecan be used wherein the long axis of the pipe runs substantiallyparallel to the long axis of the submergible conveyor (or at a slightlyoff-set angle—e.g. 5-10 degrees), and the pipe defines an open side orslot opposite from the underside of the submergible conveyor, thusallowing undersized materials to fall through the opening/slot andcollect in the pipe. Frequency of removal of undersized materials from acollection element depends upon frequency of operation of the disclosedapparatus, but is ideally carried out at regular time intervals when theapparatus is operated frequently. Regular time intervals may include,for example, at a frequency of once per day when the disclosed apparatusand/or system is operated daily.

In embodiments comprising a self-cleaning conveyor, a delivery means canfurther be disposed between a self-cleaning conveyor and a collectionelement to deliver undersized materials to a collection element. Suchdelivery means can be, for example, a bypass line configured to deliverundersized materials to a collection tank and/or to other downstreamapparatuses and/or systems. In one embodiment, the collection elementcan be directly or indirectly connected to other downstream apparatusesand/or systems to enable undersized materials to be processed separatelyor integrated with other materials for further processing. In anotherembodiment, the collection element can divert undersized materials sothat they combine with second reduced-size battery material from asecond submergible comminuting device.

In one embodiment, the submergible conveyor is a self-cleaning chainconveyor. In an embodiment, the self-cleaning chain conveyor is formedfrom a metal mesh having openings through which particles having a sizeof less than about 5 mm, or less than about 1-2 mm, for example, canpass. Use of self-cleaning chain conveyors provide particular advantagesover use of other types of self-cleaning conveyors, including providingflexibility in allowing a user to select a desired mesh size.

In embodiments comprising a self-cleaning screw conveyor, the bottom ofthe housing for the screw conveyor can comprise a filtering element(e.g. grate or screen) that undersize materials can pass through to thecollection element (e.g. pipe having an open side/slot, running alongthe length of the pipe).

In another embodiment, the first submergible comminuting device of anapparatus can be selected from a multi-shaft shredder, a hammer mill, ajaw crusher, a cone crusher, or a roll crusher and/or a secondsubmergible comminuting device is selected from a multi-shaft shredderor a granulator. In another embodiment, both the first submergiblecomminuting device and the second submergible comminuting device is amulti-shaft shredder. In another embodiment, the first submergiblecomminuting device is a quadruple-shaft shredder (for example, UNTHA'sRS100 could be modified to render it submergible via addition ofappropriate water-tight seals, etc.). In yet another embodiment, thesecond submergible comminuting device is a dual-shaft shredder or aquadruple-shaft shredder. For instance, the second submergiblecomminuting device could be a quadruple-shaft shredder such as UNTHA'sRS50

In embodiments comprising multi-shaft shredders, battery materials aretop fed through sets of semi-sharp blades configured to cause a sizereduction in the battery materials. Multi-shaft shredders may have oneset of semi-sharp blades, such as in dual-shaft shredders (also known asdual shaft or twin-shaft shredders), or may have two sets of semi-sharpblades, such as in typical quadruple-shaft shredders.

As will be known to those of skill in the art, dual-shaft shredders aretop fed with two sets of semi-sharp blades disposed on shafts rotatingtoward each other to pull material through the center. As materialtravels through the center it is sheared apart by the blades. The mainadvantages of dual-shaft shredders over quadruple-shaft shredders arethat they require less energy and space. Embodiments having dual-shaftshredders provide additional advantages including requiring lesselectrical power to operate compared to embodiments havingquadruple-shaft shredders.

As will also be known to those of skill in the art, quadruple-shaftshredders are top fed with four sets of semi-sharp blades disposed onshafts rotating toward the center. The outer two shafts help pushmaterial toward the inner shafts. The inner two shafts pull materialthrough the center. As material travels through the center it is shearedapart by the blades. There are also screens available for theseshedders; any oversized material can be swept up by the blades andre-shred. The main advantages of quadruple-shaft shredders overdual-shaft shaft shredders are that they tend to produce a more uniformparticle size and the outer shafts help clean the inner shafts.

In another embodiment, the battery materials of the first type arerechargeable lithium-ion batteries. Rechargeable lithium-ion batteriescan be large format lithium-ion batteries or small format lithium-ionbatteries. Large format lithium-ion batteries can be, for example,lithium-ion batteries measuring from about 370 mm×about 130 mm×about 100mm to about 5000 mm×about 2000 mm×about 1450 mm in size (or volumeequivalents; expressed as a rectangular prism for simplification ofgeometry), and can include electric car batteries or batteries used instationary energy storage systems. Small format lithium-ion batteriescan be, for example, batteries measuring up to about 370 mm×about 130mm×about 100 mm in size (or volume equivalents; expressed as arectangular prism for simplification of geometry), and can includeportable lithium-ion batteries such as those from cell phones, laptops,power tools or electric bicycles. Large format batteries are generallyknown in the art to be larger than small format batteries. In anotherembodiment, the battery materials can comprise battery parts as opposedto whole batteries; however, the apparatus, system, and processdescribed herein are particularly suited to processing whole batteries.In one embodiment, the battery materials of the first type are largeformat rechargeable lithium-ion batteries.

In another embodiment, the apparatus comprises a second feed chute (e.g.hopper) defining an opening therein for receiving battery materials of asecond type into the housing wherein the apparatus further comprisesmeans for delivering the battery materials of the second type from thesecond feed chute directly to the second submergible comminuting device,and wherein the second submergible comminuting device is configured tocause a size reduction in the battery materials of the second type.Battery materials of the second type can be rechargeable lithium-ionbatteries selected from large format lithium-ion batteries or smallformat lithium-ion batteries as described above. In another embodiment,the battery materials of the first type and the battery materials of thesecond type are rechargeable lithium-ion batteries. Battery materials ofthe first type and of the second type can be rechargeable lithium-ionbatteries and can be independently selected from large formatlithium-ion batteries or small format lithium-ion batteries as describedabove. In another embodiment, battery materials of the second type areof a reduced size relative to the battery materials of the first type.For example, battery materials of the second type can be small formatlithium-ion batteries and batteries of the first type can be largeformat lithium-ion batteries as described above.

The apparatus further comprises an outlet for discharging comminutedmaterial produced by the second submergible comminuting device, whereinthe discharged comminuted material can report to one or more furtheroptionally submergible comminuting devices, and/or to further downstreamsystems and processes.

In another aspect, there is provided a system for carrying out sizereduction of battery materials under immersion conditions, comprising afirst submergible comminuting device to receive battery materials of afirst type, wherein the first submergible comminuting device causes asize reduction in the battery materials of the first type to form afirst reduced-size battery material; a second submergible comminutingdevice to receive the first reduced-size battery material, wherein thesecond submergible comminuting device causes a further size reduction inthe first reduced-size battery material to form a second reduced-sizebattery material; and an immersion liquid in which each of the firstsubmergible comminuting device, the second submergible comminutingdevice, the first reduced-size battery material, and the secondreduced-size battery material are submerged. The submergible comminutingdevices are as described above in respect of the apparatus.

The system comprises means for delivering the first reduced-size batterymaterial from the first submergible comminuting device to the secondsubmergible comminuting device. The delivery means can be, for example,a delivery chute extending from the output of the first submergiblecomminuting device to the second submergible comminuting device, whereingravity feed is used to deliver the first reduced-size battery materialfrom the first submergible comminuting device to the second submergiblecomminuting device.

In another embodiment, the system further comprises a submergibleconveyor as described above for delivering the first reduced-sizebattery material from the first submergible comminuting device to thesecond submergible comminuting device, wherein the submergible conveyorreceives the first reduced-size battery material from the output of thefirst submergible comminuting device and delivers the first reduced-sizebattery material to the second submergible comminuting device forfurther comminution, and wherein the submergible conveyor is submergedin the immersion liquid. In embodiments comprising a submergibleconveyor, the submergible conveyor can be a chain conveyor as describedabove, a screw conveyer as described above, or a belt conveyor. Inembodiments comprising a chain conveyor or a screw conveyor, said chainconveyor and/or screw conveyor can be a self-cleaning chain conveyor ora self-cleaning screw conveyor as described above.

In an embodiment, the system further comprises a first delivery systemfor delivering the battery materials of the first type to the firstsubmergible comminuting device. A first delivery system can comprise afirst feed chute optionally in combination with a delivery chute and/ora submerged conveyor or a submerged self-cleaning conveyor as describedabove. Alternatively, the first feed chute can deliver the batterymaterials of the first type directly to the first submergiblecomminuting device (no intervening delivery chute or submergibleconveyor is required).

In an embodiment, the system further comprises a first submergiblecomminuting device and a second submergible comminuting device whereineach causes size reduction by compression or shearing.

In an embodiment, the first submergible comminuting device is selectedfrom a multi-shaft shredder as described above, a hammer mill, a jawcrusher, a cone crusher, or a roll crusher and/or the second submergiblecomminuting device is selected from a multi-shaft shredder as describedabove or a granulator.

In an embodiment, each of the first submergible comminuting device andthe second submergible comminuting device is a multi-shaft shredder asdescribed above.

In an embodiment, the first submergible comminuting device is aquadruple-shaft shredder as described above.

In an embodiment, the second submergible comminuting device is adual-shaft shredder as described above or a quadruple-shaft shredder asdescribed above.

In an embodiment, the battery materials of the first type arerechargeable lithium-ion batteries as described above.

In an embodiment, the system further comprises a second delivery systemfor delivering battery materials of a second type to the secondsubmergible comminuting device, wherein the second submergiblecomminuting device causes a size reduction in the battery materials ofthe second type to form a comminuted material that is submerged in theimmersion liquid and combines with the second reduced-size batterymaterial. A second delivery system can comprise a second feed chuteoptionally in combination with a delivery chute and/or a submergedconveyor or a submerged self-cleaning conveyor as described above.

In an embodiment, the battery materials of the first type and thebattery materials of the second type are rechargeable lithium-ionbatteries as described above.

In an embodiment, the battery materials of the second type are of areduced size relative to the battery materials of the first type. Inthese embodiments, battery materials of a second type can be smallformat lithium-ion batteries as described above, and battery materialsof a first type can be large format lithium-ion batteries as describedabove.

In an embodiment, the immersion liquid is an aqueous solution.

Advantages gained by use of an immersion liquid include providing ameans for absorbing heat released during battery material comminution toprovide an inherently safe system during operation by a user. Additionaladvantages are provided in embodiments comprising an aqueous solutionimmersion liquid comprising of calcium hydroxide (Ca(OH)₂) when usedwith lithium-ion battery materials due to hydrolysis of lithium-ionbattery electrolyte salts, such as LiPF₆, upon exposure to water oraqueous solutions to produce, for example, aqueous hydrogen fluoride atrates of reaction above 70° C. (S. F. Lux, I. T. Lucas, E. Pollak, S.Passerini, M. Winter and R. Kostecki, “The mechanism of HF formation inLiPF₆ based organic carbonate electrolytes,” ElectrochemistryCommunications, vol. 14, pp. 47-50, 2012). Addition of dilute levels ofhydrated lime or calcium hydroxide (Ca(OH)₂) to the aqueous immersionliquid can result in a reduction in the corrosiveness of aqueoushydrogen fluoride as aqueous fluorine may advantageously be captured asinsoluble calcium fluoride (H. G. McCann, “The solubility offluorapatite and its relationship to that of calcium fluoride,” Archivesof Oral Biology, vol. 13, no. 8, pp. 987-1001, 1968).

In an embodiment, the aqueous solution immersion liquid alternatively oradditionally comprises a salt, such as an alkali metal chloride,alkaline earth metal chloride, or mixtures thereof (e.g. sodiumchloride, calcium chloride, or mixtures thereof). Addition of a salt,such as sodium chloride (NaCl), to the aqueous solution immersion liquidprovides additional advantages when the system is used with lithium-ionbattery materials, wherein a salt can act as a conductive medium throughwhich residual charge from lithium-ion batteries can dissipate and heatreleased during battery material comminution can be absorbed to providean inherently safe system during operation by a user.

In an embodiment, the system further comprises a third comminutingdevice to receive comminuted battery materials from the secondsubmergible comminuting device, wherein the third comminuting device isoptionally submergible in the immersion liquid and causes a sizereduction of the comminuted battery materials received from the secondsubmergible comminuting device. A third comminuting device may beintegrated with systems for further processing of further comminutedbattery materials. In these embodiments, a third comminuting device canbe selected from a multi-shaft shredder as described above, asingle-shaft shredder, or a granulator. In some embodiments, a thirdcomminuting device is a submergible dual-shaft shredder or single-shaftshredder. Additional benefits may be provided in embodiments comprisinga third comminuting device wherein further size reduction of comminutedbattery materials is desired. For example, a user may desire suchfurther size reduction wherein a first submergible and/or secondsubmergible comminuting device as herein disclosed fails to produce acomminuted material having a particle size smaller than 100 mm. Forinstance, comminuted materials exiting the third comminuting device canhave a particle size of from about 40 mm to about 100 mm.

In further embodiments, the system further comprises a fourthcomminuting device to receive comminuted battery materials from thethird optionally submergible comminuting device, wherein the fourthcomminuting device is optionally submergible in the immersion liquid andcauses a size reduction of the comminuted battery materials receivedfrom the third submergible comminuting device. A fourth comminutingdevice may be integrated with systems for further processing of furthercomminuted battery materials. In one embodiment, the fourth comminutingdevice can be selected from a multi-shaft shredder as described above,or a granulator. In some embodiments, a fourth comminuting device is agranulator that is not submerged in the immersion liquid. In oneembodiment, comminuted materials exiting the fourth comminuting devicecan have a particle size of less than about 40 mm.

In another embodiment, the third and/or fourth comminuting device couldbe a dual shaft shredder such as the Franklin Miller TM2300.

For example, comminuted battery materials exiting the second submergiblecomminuting device can be optionally screened, where undersized solidsthat are at or below a first (i.e. selected) size (e.g. ≤10 mm) passthrough a screen; and, oversized solids that are a second size (i.e.oversize; larger than first (i.e. selected) size; e.g. ≤100 mm to ≥10mm) report to the third and/or fourth optionally submergible comminutingdevice for further size reduction. The solids that are at or below afirst (i.e. selected) size (e.g. ≤10 mm) undergo solid-liquid separationand further processing according to the Process described above. Furthercomminution via the third and/or fourth optionally submergiblecomminuting device reduces the oversized (i.e. second size) solids to ator below the first (selected) size (e.g. ≤10 mm) to facilitate furtherprocessing. In another embodiment, the first (selected) size can be setat ≤40 mm.

As noted above, the submergible components of the apparatus and systemas herein described can be contained within a housing configured to holdan immersion liquid. The housing can be formed as a single piece or canbe a multi-part component, so long as the housing forms a unitarystructure that houses the submergible components of the apparatus andsystem as herein described, contains the immersion liquid in which thesubmergible components are immersed and prevents unintended leakage ofthe immersion liquid to an external environment.

In embodiments of the system, the immersion liquid may be in fluidcommunication with additional systems (open loop system), or it may becomprised in a closed loop system fluidly isolated from other systems(closed loop system). For example, discharged immersion liquid from thecomminuting devices can be re-cycled back to the housing for use in thesize-reduction of battery materials under immersion conditions.Alternatively or additionally, discharged immersion liquid from thecomminuting devices can be used in downstream processes such as in thewet magnetic separation process as described above.

The disclosed apparatus and system described herein provides advantagesover apparatuses and systems known in the art, wherein energy releasedduring size reduction of battery materials submerged in an immersionliquid as described above is absorbed as heat by the immersion liquidwhich results in minimized risk of combustion and enhanced safety whenoperating the disclosed apparatus and/or system. Prior art sprayingsystems may mitigate some of the risk of combustion; however, it isbelieved that the system and apparatus as described herein whichprovides for size reduction of battery materials under immersionconditions offers enhanced safety in battery reduction operations.Further, as the skilled worker will appreciate, submersion of batterymaterials, submergible comminuting devices and, in particularembodiments, submergible conveyors in an immersion liquid provideadditional advantages of enabling a user to capture valuable batterycomponents, such as organics (i.e. alkyl carbonates), due to release ofsuch battery components into the immersion liquid during size reductionby the submergible comminuting devices. The apparatus and system asherein disclosed provides further advantages from minimizing hazardousdust release into air surrounding components of an apparatus and/orsystem as herein disclosed during size reduction of battery materials.For instance, use of the apparatus and system as described herein canmitigate the need for special ventilation systems and baghouses orfilters to deal with dust and off-gases, etc.

As will be further appreciated by the skilled worker, the embodiments ofthe apparatus and system described herein that can receive and processbattery materials of a first and second type are particularlyadvantageous, in that they allow the user to process battery materialsof different types and sizes using a single apparatus/system.

EXAMPLES

To gain a better understanding of the application as described herein,the following examples are set forth. It should be understood that theseexamples are for illustrative purposes only. Therefore, they should notlimit the scope of this application in any way.

Example 1—Exemplary Embodiment of Process 1

The following example describes phases, steps, design criteria, andIDEAS process simulation parameters (IDEAS Bronze, Mineral Processingpackage, v6.0.0.995) of said process for recovering materials fromrechargeable lithium-ion batteries.

Phase 1: Feed Size Reduction

Incoming large format lithium-ion batteries (e.g. automotive, energystorage system battery packs) and small format lithium-ion batteries(e.g. from laptops, mobile phones, tablets, etc.) are optionallydischarged to approximately between 1.0 to 2.0 V, or to approximately 0V prior to any mechanical treatment. Discharged energy optionallyreports to a central electrical storage bank, which provides peak loadreduction for, for example, plant facility-wide power consumption.Discharging lithium-ion batteries facilitates controlling energyreleased during possible short circuiting events wherein the batteries'anode(s) and cathode(s) come into contact during a battery dismantling,or multi-stage crushing/shredding step.

Multi-stage crushing/shredding is achieved via use of, for example,crushers under water/aqueous solution immersion, such as water or brineimmersion. Water/aqueous solution immersion helps ensure that sparkingcaused by crushing/shredding is suppressed and absorbed as heat by thewater/aqueous solution. Further, the presence of water/aqueous solutioncan restrict accumulation of oxygen, thereby minimizing combustion riskduring crushing.

Moreover, water/aqueous solution promotes entrainment of batteries'electrolyte (e.g., LiPF₆ in organic solvent(s)) as it is released afterlithium-ion battery crushing, facilitating an increase in overalllithium recovery. Battery electrolytes, such as LiPF₆ salt, have apotential for hydrolysis when exposed to water or aqueous solutions;however, with respect to the LiPF₆ salt for example, this typicallyoccurs above 70° C. As such, a target water/aqueous solution temperaturefor the dismantling/crushing step is, for example, approximately 60° C.to facilitate prevention of any appreciable reaction chemistry.

The crushing/shredding step helps mechanically separate the batteries,and may reduce downstream energy consumption and facilitate optimizingequipment sizing. Moreover, multi-stage size reduction facilitatesreduction of variability in particle size distribution, whichfacilitates leaching of target metals/materials.

When multi-stage crushing/shredding is used to dismantle/crush thebatteries, the multi-stage crushing comprises first crushing largeformat lithium-ion batteries to reduce their size (i.e., feed size) toapproximately ≤400 mm; and, second, crushing small format lithium-ionbatteries (when present) and the size-reduced large format lithium-ionbatteries, and reducing that feed to an approximate size of ≤100 mm toform a crushed/shredded slurry. Example operational parameters forcrushers suitable for said multi-stage crushing/shredding are providedin Table 2.

The crushed/shredded slurry is optionally screened, where undersizedsolids that are ≤10 mm pass through a screen; and, oversized solids thatare ≤100 mm to ≥10 mm report to shredding for further size reduction.The ≤10 mm solids undergo solid-liquid separation, such as via a beltfilter. Following said separation, the isolated solids optionally reportto an intermediate hopper for storage prior to magnetic separation; thesolid-liquid separation filtrate is optionally recycled back to thecrushers; and, a portion of the recycle stream is optionally bled to adownstream leach tank to facilitate an increase in overall materialsrecovery and for background impurity level control. Shredding reducesthe oversized solids to ≤10 mm to facilitate magnetic separation. Theshredded stream then optionally reports to a self-cleaning conveyor,which optionally conveys to a hopper for storage prior to magneticseparation. As used herein, the term “self-cleaning-conveyor” refers toa conveyor having a collection pipe underneath the conveyor with a slotor other opening to collect fine particles that accumulate in theconveyor. Periodically, the collection pipe is sucked clean using avacuum or similar mechanism, or fine particles collected in thecollection pipe can be diverted to downstream processes.

Generally, the combined size-reduced solids are approximatelydistributed as follows: a coarse solid fraction (≥3 mm) including, butnot limited to shredded steel and/or aluminum casing, any electricalcomponents, plastic, copper cable, aluminum cathode foil, copper anodefoil and possibly paper; and, a fine solid fraction (which can be assmall as ≤0.5 mm) including anode powder and cathode powder.

Table 2 delineates example design and IDEAS process simulationparameters for the Phase 1 feed size reduction steps.

Phase 2: Leaching and Intermediate Product Preparation

The optionally screened dismantled/crushed slurry from Phase 1 ismagnetically separated by reporting to, for example, a magneticseparator; example operational parameters of which are provided in Table3. Magnetic/ferrous materials (e.g. steel sheet; ferrous product(s)) areseparated from non-magnetic/non-ferrous materials via wet magneticseparation. Magnetic separation consists of a rougher step and anoptional cleaner step, depending on incoming feed and separationefficiency. The magnetic (‘mag’) stream separated from the magneticseparator undergoes solid-liquid separation by reporting to, forexample, a dewatering screen; and produces a shredded steel or ferrousproduct. The separated water/aqueous solution is optionally recycledback to the magnetic separator for use as make-up water/aqueoussolution, and a portion of the recycled stream is optionally bled to adownstream leach tank. Bleeding/sending a portion of the recycled streamto the leach tank may facilitate impurity control in the magneticseparator and dewatering screen circuit: if a portion of the recyclestream is not bled, there could be build-up of fine particles and/orspecies formed from side reaction chemistry (e.g. trace levels ofprecipitates) in a circuit's piping, potentially leading to plugging,down-time and production loss.

A non-magnetic/non-ferrous (‘non-mag’) stream from magnetic separationundergoes further separation via eddy current separation by reportingto, for example, an eddy current separator to separate any residualmagnetic/ferrous material, and isolate an aluminum product stream priorto a leaching step. Generally, aluminum product(s) is separated prior toleaching to reduce unnecessary reagent consumption, etc. During eddycurrent separation, separated residual magnetic/ferrous materialoptionally reports to a dewatered solid hopper that collects materialfrom the upstream solid-liquid separation (e.g. belt filter).

Generally, the separated non-magnetic/non-ferrous stream comprisesaluminum and some copper. Depending on compositions of thenon-magnetic/non-ferrous stream from eddy current separation, anoptional densimetric table or analogous unit operation may be used tofurther separate the aluminum and copper streams. Optionally, separatedcopper is subjected to acid leaching; or, depending on product quantityand quality, the copper optionally reports to a dewatering screen forcollection and storage as a final product.

The aluminum product stream from eddy current separation optionallyreports to a dewatering screen to isolate an aluminum product (e.g.,shredded aluminum). For example, the dewatering screen is a linearvibrating screen (e.g., a screen having counter rotating motors thatcreate a linear motion to move solids downhill while water/aqueoussolution drains through screen media). The separated water/aqueoussolution is optionally recycled back to the magnetic separator for useas make-up water/aqueous solution, and a portion of the recycled streamis optionally bled to the leach tank.

The remaining eddy current-separated, non-magnetic/non-ferrous streamcomprises at least one of electrode (e.g. metal oxide cathode powders,graphite anode), paper, plastic, and some residual non-ferrous (e.g.shredded copper and/or aluminum) components. This stream reports to aleach tank for leaching.

Table 3 delineates example design and IDEAS process simulationparameters for Phase 2 magnetic separation and eddy current separation.

Leaching is optionally conducted in a series of tanks, for exampleconical-bottom tanks under high shear agitation; or, a sloped or flatbottom tank. A conical, sloped, or flat bottom tank promotes settling ofhigher-density, coarse solid fractions. Agitation helps ensure that highvalue fine fractions are suspended and promotes leaching kinetics.Multiple tanks optimize leaching reaction kinetics and provideoperational redundancy. Sulfuric acid is optionally used to leach targetmetals/materials in the influent slurries. Hydrogen peroxide and oxygengas are optionally added to reduce and oxidize nobler metals to increaseextraction rates; further, for example, hydrogen peroxide addition mayincrease extraction of copper, cobalt, etc. but decrease nickelextraction. Alternatively, hydrochloric acid is used; or, nitric acidwith or without hydrogen peroxide.

Several influent streams optionally report to leaching:non-magnetic/non-ferrous stream from eddy current separation (excludingthe majority of aluminum product(s)); leaching reagents, such as acid,hydrogen peroxide, etc.; and, bleed and recycle streams fromupstream/downstream steps.

The leached slurry is optionally screened to remove a majority of acoarse size fraction, before reporting to countercurrent decantation.The screening is completed using, for example, a wet screen. Saidscreens are used to screen out fine and undersized particles; in someinstances, the wet screens include make-up water/aqueous solution spraysto facilitate screening. Undersized solids that are approximately ≤5 mmin size pass through the screen and report to countercurrent decantation(CCD). Oversized solids that are approximately ≥5 mm are optionallyrecycled to magnetic separation for further processing. Screeningfacilitates separating coarse particles prior to CCD, thereby minimizingequipment wear.

Countercurrent Decantation (CCD) is a solid-liquid separation processthat is achieved via settling, optionally with make-up processwater/aqueous solution added as a wash medium. The purpose of CCD is toseparate slimes/residues (e.g., wet solid material that is residualafter processing) from the leaching step from a liquid phase consistingof aqueous leachate, organics (i.e. residual alkyl carbonates) andfloating graphite.

Optionally, CCD consists of several thickeners in sequence, withcountercurrent flows for underflow and overflow streams. Thickenersfunction on a principle of gravity sedimentation: an inlet feed is fedto the center of a tank via a feed well, where a suspended series ofblades function to rake any settled solids towards a central outlet,i.e. the underflow. The blades also assist the compaction of settledparticles and produce a thicker underflow than would be achieved bysimple gravity settling. Solids in the thickener move downwards and theninwards towards the central underflow outlet. Liquid moves upwards andradially outwards to a launder/collection area where they exit as theoverflow. Examples of thickeners potentially suitable for use in CCDinclude: (1) high-rate type, (2) rakeless ultra high-rate type, (3)traction type, (4) high-density type, and (5) deep cone type.

A countercurrent arrangement helps ensure that the most concentratedportion of either the underflow or overflow streams is in contact withthe least concentrated portion of the other stream, potentially reducinglosses of soluble metals. The final overflow of CCD optionally reportsto an agglomeration tank for subsequent separation of a graphite product(e.g., graphite concentrate). The final underflow of CCD reports tosolid-liquid separation; for example, a belt filter for solid-liquidseparation of the slimes and production of a copper product (e.g.,copper concentrate).

Table 4 delineates example design and IDEAS process simulationparameters for Phase 2 leaching and CCD steps. Table 5 delineates keyreaction chemistry for the Phase 2 leaching step per the IDEAS processsimulation parameters.

The anode/graphite powder, electrical components, organic component ofthe electrolyte, plastic, and any residual steel casing are potentiallyrelatively unreactive during the leaching step. Generally, theseinfluent components partition between the overflow and underflow fromCCD as follows: most of the shredded copper, electrical components, anyresidual steel and aluminum, and some of the graphite, plastic, paper,and organic materials (i.e. residual alkyl carbonates) from the feedlithium-ion batteries' electrolyte may report to the CCD underflow; and,an aqueous pregnant leach solution (PLS), containing soluble metals perTable 1, most of the graphite (e.g., ≥90% of graphite), plastic, paper,and organic materials from the feed lithium-ion batteries' electrolyte(e.g., ≥70% of paper, plastics; and ≥95% of organics) may exit with thefinal CCD overflow.

The final CCD overflow reports to an agglomeration tank. Graphiteagglomerates, optionally via added flocculant (e.g., semi-hydrophobic orhydrophobic polymeric flocculants; for example, a polyethyleneoxide-based flocculant), to assist in graphite isolation. Theagglomeration tank solution report to a flotation cell(s) to selectivelyseparate hydrophobic components (e.g., graphite agglomerated withflocculant, organics (i.e. residual alkyl carbonates)) from hydrophiliccomponents (e.g., pregnant leach solution). The flotation cell(s) usesair, or other gases (e.g., noble gases, N₂, etc.) to produce bubbles;hydrophobic particles attach to the bubbles and rise to the surface,forming a froth. Other options for graphite isolation include spiralseparator(s), or jig concentrator(s).

Flotation optionally takes place over two stages to maximize separationand recovery: a rougher flotation and a cleaner flotation. Rougherflotation separates a maximum amount of hydrophobic components from thepregnant leach solution (PLS). The rougher froth reports to a cleaningstage for further flotation. The rougher flotation residue/PLSoptionally reports to a holding tank to be mixed with the cleanerflotation residue/PLS for downstream processing. Cleaner flotationfurther separates the rougher froth to isolate hydrophobic componentsfrom the hydrophilic pregnant leach solution (PLS). The isolated frothundergoes solid-liquid separation by reporting to, for example,downstream centrifugation to isolate the graphite product (e.g.,graphite concentrate). Filtrate from the solid-liquid separationoptionally reports to a holding tank before optionally reporting to adual media filter or belt filter for entrained organic (i.e. alkylcarbonates) and fine and coarse suspended solids removal. The cleanerflotation residue/PLS optionally reports to a holding tank, and is thenmixed with the rougher flotation residue/PLS to optionally report to adual media filter or belt filter for entrained organic (i.e. alkylcarbonates) and fine and coarse suspended solids removal.

The PLS from the flotation step(s) and the filtrate from thesolid-liquid separation optionally report to a dual media filter; afilter similar to that generally found in solvent extractionapplications. A first media layer (for example, sand, anthracite)removes entrained organics (e.g. alkyl carbonates such as ethylenecarbonate/EC and/or ethyl methyl carbonate/EMC) from the PLS, while asecond media filter (for example, garnet, sand, anthracite) removes finesuspended solids. The filtered PLS then optionally reports to a holdingtank before being processed through copper-ion exchange or solventextraction (see, for example, Table 7). Recovered organics (i.e. alkylcarbonates) from dual media filtration can optionally be collected, etc.A media backwash outlet stream (e.g., process water/aqueous solution andany residual fine particulates, such as residual graphite, fine plasticsentrained by the second media layer, and minimal entrained organics) isoptionally recycled to water/aqueous solution treatment facilities andreused as make-up water/aqueous solution for the herein describedprocess. Optionally, the liquid stream from the dual media filterreports to an activated carbon filter for polishing removal of entrainedorganics, as needed. Alternatively, a belt filter can be used to removeany remaining oversize solids from upstream and downstream processes.The filtrate optionally reports to a holding tank before reporting tocopper ion exchange, or solvent extraction.

Table 6 delineates example design and IDEAS process simulationparameters for the Phase 2 intermediate product preparation steps.

Phase 3: Final Product Preparation

A graphite product (e.g., graphite concentrate) is isolated viasolid-liquid separation; for example, via centrifugation of the cleanerfroth of Phase 2 flotation. The graphite product is potentially mixedwith some plastic and paper, and may be further purified via: (i) lowtemperature chemical treatment involving multi-stage acid washing (e.g.using sulfuric or hydrochloric acid) to remove impurities/soluble metals(e.g. residual soluble metals such as lithium, nickel, cobalt, copper,and/or manganese) to produce a higher purity graphite concentrate;and/or (ii) thermal purification, e.g., raising the temperature of theconcentrate via pyrometallurgical methods (e.g. using a furnace to raisethe graphite temperature to ˜1000 to 2000° C.) to volatilize specificconstituents (e.g., residual organic and plastics) to produce a higherpurity graphite product.

The final underflow of CCD/slimes are solid-liquid separated to form acopper product (e.g., a copper/Cu⁰ concentrate that may be mixed withresidual plastic, paper, graphite, minimal aluminum and steel content).The optionally dual media filtered PLS reports to a copper-ion exchangefor selective separation of copper from the inlet stream (see, forexample, Table 7). The eluate/copper-rich liquor reports to copperelectrowinning (e.g., conventional electrowinning, Emew® electrowinning,etc.) for deposition of copper/Cu⁰ as a copper plate. Spent electrolytefrom the electrowinning is optionally recycled to the copper-ionexchange for use as a regenerant, as applicable, with a portion of therecycle stream being optionally bled to the upstream leach tank.

Alternatively, copper/Cu⁰ is deposited via a copper solvent extractionand copper electrowinning when the PLS copper concentration is, forexample, approximately 5 g/L. The copper solvent extraction optionallyconsists of extraction stage(s) consisting of mixer-settler(s) (e.g.,each mixer settler consisting of 1-2 mixer stage(s) and 1 settlerstage), potential wash stage(s) consisting of mixer-settler(s) (e.g.,each mixer-settler consisting of 1-2 mixer stage(s) and 1 settlerstage), and stripping stage(s) consisting of mixer-settler(s) (e.g.,each mixer-settler consisting of 1-2 mixer stage(s) and 1 settlerstage). As needed, make-up acid is added to the influent PLS toappropriately adjust pH for optimal copper extraction. The extractionmixer-settler stage(s) utilize an organic extractant (such as ketoxime[e.g. LIX® 84], salicylaldoxime, or a mixture ofketoxime-salicylaldoxime organic extractants) in a diluent (e.g. inkerosene) to selectively extract copper into the organic phase:

CuSO_(4(aq))+2HR_((org))→CuR_(2(org))+H₂SO_(4(aq))  Extraction:

The copper-loaded organic phase then reports to the stripping stage(s)where the extracted copper ions are stripped back into the aqueousphase; for example, using spent electrolyte from copper electrowinningcontaining acid (e.g., sulfuric acid/H₂SO₄):

CuR_(2(org))+H₂SO_(4(aq))→CuSO_(4(aq))+2HR_((org))  Stripping:

If hydrochloric acid is utilized for pH adjustment, instead of sulfuricacid, optional wash stage(s) are included to minimize levels ofentrained aqueous phase containing chloride in the organic phase. Thepregnant strip liquor (e.g. at a concentration of approximately 50 g/Lsoluble copper) then reports to copper electrowinning to depositcopper/Cu⁰ as a copper plate on a cathode sheet. Once the plate reachesa desired copper thickness, it is removed and optionally replaced withan empty cathode sheet. Spent electrolyte from copper electrowinning isoptionally recycled back to the stripping stage(s) of copper solventextraction; and, the organic phase is optionally recycled back to theextraction stage(s) for reuse, with polishing as needed.

The copper-stripped liquor reporting from copper electrowinning is then:reacted with a hydroxide (e.g., sodium hydroxide, hydrated lime/calciumhydroxide, etc.) to precipitate a Co, Ni, and/or Mn hydroxide product;reacted with a carbonate (e.g., sodium carbonate) to precipitate a Co,Ni, and/or Mn carbonate product; evaporative crystallized to form a Co,Ni, and/or Mn sulfate product; or, reacted with a hydroxide (e.g.,sodium hydroxide, hydrated lime/calcium hydroxide, etc.) to precipitatea Co, Ni, and/or Mn hydroxide product, followed by thermal dehydrationto produce a Co, Ni, and/or Mn oxide product (e.g., cobalt (II, III)oxide, Co₃O₄, nickel (II) oxide, NiO, manganese (IV) dioxide, MnO₂). TheCo, Ni, and/or Mn product then reports to solid-liquid separation, and asolid filter cake is collected. With respect to the Co, Ni, and/or Mnsulfate product, once the copper-stripped liquor from copperelectrowinning reports to an evaporative crystallizer, the resultingproduct consists of a mixture of cobalt sulfate heptahydrate/CoSO₄.7H₂O,nickel sulfate hexahydrate/NiSO₄.6H₂O, and manganese sulfatemononydrate/MnSO₄.H₂O. The crystallized slurry then reports to, forexample, solid-liquid separation (e.g., centrifuge or filter press),followed by a drier to drive off excess water.

The Co, Ni, and/or Mn solid-liquid separation filtrate is then reactedwith a carbonate (e.g., sodium carbonate, etc.) to precipitate lithiumcarbonate/Li₂CO₃. This lithium carbonate product optionally undergoessolid-liquid separation (e.g., centrifugation) and a solid cake iscollected. To optionally further purify the lithium carbonate, itreports to an ion exchange column to remove trace impurities such ascalcium and magnesium (see, for example, Table 7); and then, to abicarbonation circuit where carbon dioxide is bubbled into, for example,a dissolution/digestion tank to convert the lithium carbonate into moresoluble lithium bicarbonate before being recrystallized into a higherpurity lithium carbonate slurry. The slurry is then solid-liquidseparated to give high purity lithium carbonate/Li₂CO₃ and is optionallydried.

Alternatively, the Co, Ni, and/or Mn solid-liquid separation filtrate isreacted with a hydroxide (e.g., sodium hydroxide, hydrated lime/calciumhydroxide, etc.) to form a lithium hydroxide and sodium sulfatesolution. The lithium hydroxide and sodium sulfate solution reports tocrystallization (e.g. using a draft tube baffle crystallizer) to coolthe solution and produce a slurry including sodium sulfate decahydratecrystals and soluble lithium hydroxide. The slurry from crystallizationreports to solid-liquid separation (e.g. using centrifugation) toseparate a solid sodium sulfate decahydrate product and a filtratecomprising lithium hydroxide in solution. The lithium hydroxide solutionfrom solid-liquid separation is evaporative crystallized: the lithiumhydroxide monohydrate is crystallized using, for example, a tripleeffect crystallizer; then, solid-liquid separated via, for example,centrifugation. The product is optionally further purified by dissolvingthe lithium hydroxide monohydrate crystals in pure water (e.g.,distilled or deionized water) and recrystallizing them (e.g. using amechanical vapour recompression (MVR) crystallizer), followed byoptional solid-liquid separation (e.g. using a centrifuge) to collectthe purified lithium hydroxide monohydrate product. The lithiumhydroxide monohydrate crystals are optionally dried.

Sodium sulfate is optionally isolated as a product. The sodium sulfatesolution formed from reacting the Co, Ni, and/or Mn solid-liquidseparation filtrate with a base (e.g., a hydroxide) is isolated andoptionally crystallized to give sodium sulfate decahydrate. Thiscrystallization is achieved by cooling the sodium sulfate solution in acrystallizer, such as draft tube baffle crystallizers, following whichthe crystals are optionally dried and cooled. Alternatively, oradditionally, the centrate from the Li₂CO₃ solid/liquid separation(e.g., centrifugation) reports to an evaporative crystallizer to producesodium sulfate decahydrate/Na₂SO₄.10H₂O. Sulfuric acid is optionallyadded during said crystallization to convert any residual carbonate(e.g. Na₂CO_(3(aq))) into a sulfate form. The resulting crystallizedslurry is solid-liquid separated (e.g., centrifuged), and the separatedsolid product reports to a drier (e.g., a flash drier). The drier drivesoff water and produces anhydrous sodium sulfate/Na₂SO₄.

Table 7 delineates example design parameters; and Table 8 delineates keyreaction chemistry for the Phase 3 final product preparation steps, perthe IDEAS process simulation mode results.

Example 2—Exemplary Embodiment of Process 2

In particular, the following example describes phases, steps, designcriteria, and IDEAS process simulation parameters (IDEAS Bronze, MineralProcessing package, v6.0.0.995) of said process for recovering materialsfrom rechargeable lithium-ion batteries.

Phase 1: Feed Size Reduction (e.g. Steps (i) and (i)(a) of FIG. 1B)

As in Process 1 above, incoming large format lithium-ion batteries (e.g.automotive, energy storage system battery packs) and small formatlithium-ion batteries (e.g. from laptops, mobile phones, tablets, etc.)are optionally discharged to approximately between 1.0 to 2.0 V, or toapproximately 0 V prior to any mechanical treatment. Discharged energyoptionally reports to a central electrical storage bank, which providespeak load reduction for, for example, plant facility-wide powerconsumption. Discharging lithium-ion batteries facilitates controllingenergy released during possible short-circuiting events wherein thebatteries' anode(s) and cathode(s) come into contact during a batterydismantling, or multi-stage crushing/shredding step.

Multi-stage crushing/shredding is achieved via use of, for example,crushers under water/aqueous solution immersion, such as water or brineimmersion. Water/aqueous solution immersion helps ensure that sparkingcaused by crushing/shredding is suppressed and absorbed as heat by thewater/aqueous solution. Further, the presence of water/aqueous solutioncan restrict accumulation of oxygen, thereby minimizing combustion riskduring crushing.

Moreover, water/aqueous solution promotes entrainment of batteries'electrolyte (e.g., LiPF₆ in organic solvent(s)) as it is released afterlithium-ion battery crushing, facilitating an increase in overalllithium recovery. Battery electrolytes, such as LiPF₆ salt, have apotential for hydrolysis when exposed to water or aqueous solutions;however, with respect to the LiPF₆ salt for example, this typicallyoccurs above 70° C. As such, a target water/aqueous solution temperaturefor the dismantling/crushing step is, for example, approximately 60° C.to facilitate prevention of any appreciable reaction chemistry.

The shredding/crushing step helps mechanically separate the batteries,and may reduce downstream energy consumption and facilitate optimizingequipment sizing. Moreover, multi-stage size reduction facilitatesreduction of variability in particle size distribution, whichfacilitates leaching of target metals/materials.

When multi-stage crushing/shredding is used to dismantle/crush thebatteries, the multi-stage crushing comprises first crushing largeformat lithium-ion batteries to reduce their size (i.e., feed size) toapproximately ≤400 mm; and, second, crushing small format lithium-ionbatteries (when present) and the size-reduced large format lithium-ionbatteries, and reducing that feed to an approximate size of ≤100 mm toform a shredded/crushed slurry. Example operational parameters forcrushers suitable for said multi-stage crushing/shredding are providedin Table 2.

The crushed/shredded slurry is optionally screened, where undersizedsolids that are ≤10 mm pass through a screen; and, oversized solids thatare ≤100 mm to ≥10 mm report to shredding for further size reduction.The ≤10 mm solids undergo solid-liquid separation, such as via asettling tank. After the settling tank, the solid slurry optionallyreports to a belt filter for further solid-liquid separation.Alternatively, the isolated solids may report to an intermediate hopperfor storage prior to magnetic separation. The solid-liquid separationfiltrate is optionally recycled back to the crushers/shredders to bereused as make-up water, or optionally sent to an organic (i.e. alkylcarbonates) removal circuit. A portion of the recycle stream (eitherfrom/to the crushers/shredders or the organic removal circuit) isoptionally bled to a downstream leach tank to facilitate an increase inoverall materials recovery and for background impurity level control.Shredding reduces the oversized solids to ≤10 mm to facilitate magneticseparation. The shredded stream then optionally reports to aself-cleaning conveyor, which optionally conveys to a hopper for storageprior to magnetic separation. As used herein, the term“self-cleaning-conveyor” refers to a conveyor having a collection pipeunderneath the conveyor with a slot or other opening to collect fineparticles that accumulate in the conveyor. Periodically, the collectionpipe is sucked clean using a vacuum or similar mechanism, or fineparticles collected in the collection pipe can be diverted to downstreamprocesses.

The optional solid-liquid separation filtrate from belt filtration andthe settling tank can report to an optional dual media filter or vacuumdistillation circuit to remove any organics (i.e. alkyl carbonates). Thedual media filter contains filtration media such as anthracite, garnet,and/or sand to remove any entrained organics (i.e. alkyl carbonates) inthe filtrate. Alternatively, vacuum distillation consisting of single ormultiple stage distillation can be utilized, where aqueous content ispredominantly evaporated in a vacuum leaving an organic (i.e. alkylcarbonates) rich stream. The gaseous aqueous stream is then condensed toform a liquid aqueous stream. The aqueous stream is then optionallyeither recycled to the crushers/shredders, or bled to a downstream leachtank to facilitate an increase in overall materials recovery and forbackground impurity level control. Conducting the removal of organics(i.e. alkyl carbonates) upstream prevents chemical and mechanicalcomplications from occurring downstream due to alkyl carbonatecontamination, for example, in Phase 2 and Phase 3.

Generally, the combined size-reduced solids are approximatelydistributed as follows: a coarse solid fraction (≥3 mm) including, butnot limited to shredded steel and/or aluminum casing, any electricalcomponents, plastic, copper cable, aluminum cathode foil, copper anodefoil and possibly paper; and, a fine solid fraction (which can be assmall as ≤0.5 mm) including anode powder and cathode powder. As notedabove, undersize materials having a particle size of, for example, lessthan about 5 mm, or less than about 1-2 mm, can be collected during thefeed size reduction and diverted to downstream process steps. Forexample, such undersize materials could be collected by having theoutput of a crusher/shredder contact a metal mesh (such as on aself-cleaning conveyor as noted above) having openings sized to permitparticles having a size of less than about 5 mm or less than about 1-2mm to pass through and be collected. The undersize materials can becombined with, for example, a black mass solid stream and these combinedmaterials can then be subjected to leaching (described in further detailbelow).

Table 2 delineates example design and IDEAS process simulationparameters for the Phase 1 feed size reduction steps.

Phase 2: Intermediate Product Preparation and Leaching (e.g. Steps(ii)-(x) of FIG. 1B

The optionally screened dismantled/crushed/shredded slurry from Phase 1is magnetically separated (see step (ii) in FIG. 1B) by reporting to,for example, a magnetic separator; example operational parameters ofwhich are provided in Table 9. Magnetic/ferrous materials (e.g. steelsheet; ferrous product(s)) are separated from non-magnetic/non-ferrousmaterials via wet/dry magnetic separation. Magnetic separation consistsof a rougher step and an optional cleaner step, depending on incomingfeed and separation efficiency. The magnetic (‘mag’) stream separatedfrom the magnetic separator optionally undergoes solid-liquid separation(if wet magnetic separation is utilized) by reporting to, for example, adewatering screen; and produces a shredded steel or ferrous product(step (iii) in FIG. 1B). The separated water/aqueous solution isoptionally recycled back to the magnetic separator for use as make-upwater/aqueous solution, and a portion of the recycled stream isoptionally bled to a downstream leach tank. Bleeding/sending a portionof the recycled stream to the leach tank may facilitate impurity controlin the magnetic separator and dewatering screen circuit: if a portion ofthe recycle stream is not bled, there could be build-up of fineparticles and/or species formed from side reaction chemistry (e.g. tracelevels of precipitates) in a circuit's piping, potentially leading toplugging, down-time and production loss.

The non-magnetic/non-ferrous stream from magnetic separation reports toa series of mixing tanks (represented by stripping step (iv) in FIG.1B), where a stripping solvent is added to strip the bonded blackmass/electrode powder material from the first non-magnetic stream. Theaddition of stripping solvent, for example N-Methyl-2-pyrrolidone (otheroptions are provided in Table 9 below), dissolves the binder material,for example polyvinylidene fluoride (PVDF), and allows the electrodepowder material to coagulate into a black mass. The stripped slurrystream (i.e. black mass/electrode powder stream), undergoes solid-liquidseparation (see step (v) in FIG. 1B) by reporting to, for example, awire mesh screen with 500 μm openings, producing an oversize solidsportion of the stripped slurry stream (i.e. larger solids portion of theseparation)—comprising aluminum, copper, and plastics—and an undersizedstripped slurry stream (i.e. liquid portion of the separation containingsmaller suspended solids including black mass). The oversize solidsportion of the stripped slurry stream is optionally dried by reportingto, for example, a dewatering conveyor. The undersized stripped slurrystream reports to a filter press for solid-liquid separation (see step(vii) in FIG. 1B) to yield a liquid containing the solvent and a blackmass solid stream. The separated solvent is optionally collected into atank, and is optionally recycled back to the stripping tanks for use asmake-up solvent.

The oversize solids portion of the stripped slurry stream then canoptionally undergo further separation (per step (vi) in FIG. 1B) byreporting to, for example, a densimetric separator unit. The densimetricseparator unit optionally separates the oversize solids portion of thestripped slurry stream into three separate streams, including apreliminary aluminum product stream, a preliminary copper productstream, and a plastic product stream. The isolated streams areoptionally washed and report to a dewatering screen to collect separateand washed preliminary aluminum product, preliminary copper product, andplastic product streams.

The black mass solid stream comprises at least one of electrode (e.g.metal oxide and/or metal phosphate cathode powders, graphite anode),plastic, and some residual non-ferrous (e.g. shredded copper and/oraluminum) components. This stream reports to a leach tank for leaching,together with undersize materials having a particle size of, forexample, less than about 5 mm, or less than about 1-2 mm, from the feedsize reduction phase as described above.

Table 9 delineates example design and IDEAS process simulationparameters for Phase 2 magnetic separation, stripping, and optionaldensimetric separation.

Leaching (see step (viii) of FIG. 1B) is optionally conducted in aseries of tanks, for example conical-bottom tanks under high shearagitation; or, a sloped or flat bottom tank. A conical, sloped, or flatbottom tank promotes settling of higher-density, coarse solid fractions.Agitation helps ensure that high value fine fractions are suspended andpromotes leaching kinetics. Multiple tanks optimize leaching reactionkinetics and provide operational redundancy. Sulfuric acid is optionallyused to leach target metals/materials in the influent slurries. Hydrogenperoxide and oxygen gas are optionally added to reduce and oxidizenobler metals to increase extraction rates; further, for example,hydrogen peroxide addition may increase extraction of copper, cobalt,etc. but decrease nickel extraction. Alternatively, hydrochloric acid isused; or, nitric acid with or without hydrogen peroxide.

Several influent streams report to leaching: black mass solid streamfrom the stripping step and subsequent separation step; leachingreagents, such as acid, hydrogen peroxide, etc.; and, bleed and recyclestreams from upstream/downstream steps.

The leached slurry produced by the leaching step is subjected to asolid-liquid separation (see step (ix) in FIG. 1B), such as filtration,to produce a first product stream containing residual solids followingthe leaching step and a second product stream comprising the leachate(i.e. pregnant leach solution (PLS)).

Table 10 delineates example design and IDEAS process simulationparameters for Phase 2 leaching. Table 5 delineates key reactionchemistry for the Phase 2 leaching step per the IDEAS process simulationparameters.

The 1^(st) product stream containing residual solids following theleaching step is mixed with water, and the pH is adjusted to a pHranging between 4 and 8. The mixing tank solution reports to a flotationcell(s) to selectively separate hydrophobic components (e.g., graphite,organics (i.e. alkyl carbonates), and residual plastics) fromhydrophilic components (e.g., process mixing water). The flotationcell(s) uses air, or other gases (e.g., noble gases, N₂, etc.) toproduce bubbles; hydrophobic particles attach to the bubbles and rise tothe surface, forming a froth. Other options for graphite isolationinclude spiral separator(s), or jig concentrator(s).

Flotation optionally takes place over two stages to maximize separationand recovery: a rougher flotation and a cleaner flotation. Rougherflotation separates a maximum amount of hydrophobic components from theprocess mixing water. The rougher froth reports to a cleaning stage forfurther flotation. The rougher flotation residue/process mixing wateroptionally reports to a holding tank to be mixed with the cleanerflotation residue/process mixing water for downstream processing.Cleaner flotation further separates the rougher froth to isolatehydrophobic components from the hydrophilic process mixing water. Theisolated froth undergoes solid-liquid separation by reporting to, forexample, downstream centrifugation to isolate the graphite product(e.g., graphite concentrate). Filtrate from the solid-liquid separationoptionally reports to a holding tank before being recycled back to themixing tank.

The PLS from the solid-liquid separation optionally reports to a dualmedia filter; a filter similar to that generally found in solventextraction applications. A first media layer (for example, sand,anthracite) removes entrained organics (i.e. alkyl carbonate(s)) (e.g.ethylene carbonate/EC and/or ethyl methyl carbonate/EMC) from the PLS,while a second media filter (for example, garnet, sand, anthracite)removes fine suspended solids. The filtered PLS then optionally reportsto a holding tank before being processed through copper-ion exchange orsolvent extraction (see, for example, Table 12). Recovered organics(i.e. alkyl carbonate(s)) from dual media filtration can optionally becollected, etc. A media backwash outlet stream (e.g., processwater/aqueous solution and any residual fine particulates, such asresidual graphite, fine plastics entrained by the second media layer,and minimal entrained organics (i.e. alkyl carbonates(s)) is optionallyrecycled to water/aqueous solution treatment facilities and reused asmake-up water/aqueous solution for the herein described process.Optionally, the liquid stream from the dual media filter reports to anactivated carbon filter for polishing removal of entrained organics(i.e. alkyl carbonates), as needed. Alternatively, a belt filter may beused to remove any remaining oversize solids from upstream anddownstream processes. The filtrate optionally reports to a holding tankbefore reporting to copper ion exchange or solvent extraction.

Table 11 delineates example design and IDEAS process simulationparameters for the Phase 2 intermediate product preparation steps.

Phase 3: Final Product Preparation (e.g. Steps (xi)-(xv) of FIG. 1B

A graphite product (e.g., graphite concentrate) is isolated viasolid-liquid separation; for example, via centrifugation of the cleanerfroth of Phase 2 flotation. The graphite product is potentially mixedwith some plastic and paper, and may be further purified via: (i) lowtemperature chemical treatment involving multi-stage acid washing (e.g.using sulfuric or hydrochloric acid) to remove impurities/soluble metals(e.g. residual soluble metals such as lithium, nickel, cobalt, copper,and/or manganese) to produce a higher purity graphite concentrate;and/or (ii) thermal purification, e.g., raising the temperature of theconcentrate via pyrometallurgical methods (e.g. using a furnace to raisethe graphite temperature to ˜1000 to 2000° C.) to volatilize specificconstituents (e.g., residual organic/(i.e. alkyl carbonates) andplastics) to produce a higher purity graphite product.

The optionally dual media or belt filtered PLS reports to a copper-ionexchange for selective separation of copper from the inlet stream (see,for example, Table 12). The eluate/copper-rich liquor reports to copperelectrowinning (e.g., conventional electrowinning, Emew® electrowinning,etc.) for deposition of copper/Cu⁰ as a copper plate. Spent electrolytefrom the electrowinning is optionally recycled to the copper-ionexchange for use as a regenerant, as applicable, with a portion of therecycle stream being optionally bled to the upstream leach tank.

Alternatively, copper/Cu⁰ is deposited via a copper solvent extractionand copper electrowinning when the PLS copper concentration is, forexample, approximately 5 g/L. The copper solvent extraction optionallyconsists of extraction stage(s) consisting of mixer-settler(s) (e.g.,each mixer settler consisting of 1-2 mixer stage(s) and 1 settlerstage), potential wash stage(s) consisting of mixer-settler(s) (e.g.,each mixer-settler consisting of 1-2 mixer stage(s) and 1 settlerstage), and stripping stage(s) consisting of mixer-settler(s) (e.g.,each mixer-settler consisting of 1-2 mixer stage(s) and 1 settlerstage). As needed, make-up acid or base (e.g. sodium hydroxide) is addedto the influent PLS to appropriately adjust pH for optimal copperextraction. The extraction mixer-settler stage(s) utilize an organicextractant (such as ketoxime [e.g. LIX® 984N], salicylaldoxime, or amixture of ketoxime-salicylaldoxime organic extractants) in a diluent(e.g. in kerosene) to selectively extract copper into the organic phase:

CuSO_(4(aq))+2HR_((org))→CuR_(2(org))+H₂SO_(4 (aq))  Extraction:

The copper-loaded organic phase then reports to the stripping stage(s)where the extracted copper ions are stripped back into the aqueousphase; for example, using spent electrolyte from copper electrowinningcontaining acid (e.g., sulfuric acid/H₂SO₄):

CuR_(2(org))+H₂SO_(4 (aq))→CuSO_(4 (aq))+2HR_((org))  Stripping:

If hydrochloric acid is utilized for pH adjustment, instead of sulfuricacid, optional wash stage(s) are included to minimize levels ofentrained aqueous phase containing chloride in the organic phase. Thepregnant strip liquor (e.g. at a concentration of approximately 50 g/Lsoluble copper) then reports to copper electrowinning to depositcopper/Cu⁰ as a copper plate on a cathode sheet. Once the plate reachesa desired copper thickness, it is removed and optionally replaced withan empty cathode sheet. Spent electrolyte from copper electrowinning isoptionally recycled back to the stripping stage(s) of copper solventextraction; and, the organic phase is optionally recycled back to theextraction stage(s) for reuse, with polishing as needed.

The copper isolation raffinate (i.e. copper-stripped liquor) can thenoptionally be sparged with oxygen to gas to oxidize any ferrous (Fe²⁺)content to insoluble ferric (Fe³⁺) and subsequently optionally reactedwith a hydroxide (e.g., sodium hydroxide, hydrated lime/calciumhydroxide, etc.) to precipitate an Al and/or Fe hydroxide product. TheAl/and or Fe product could then report to solid-liquid separation and asolid filter cake would be collected.

The Al and/or Fe-depleted solution (Al and/or Fe product preparationfiltrate) is then reacted with a hydroxide (e.g., sodium hydroxide,hydrated lime/calcium hydroxide, etc.) to precipitate a Co, Ni, and/orMn hydroxide product; reacted with a carbonate (e.g., sodium carbonate)to precipitate a Co, Ni, and/or Mn carbonate product; evaporativecrystallized to form a Co, Ni, and/or Mn sulfate product; or, reactedwith a hydroxide (e.g., sodium hydroxide, hydrated lime/calciumhydroxide, etc.) to precipitate a Co, Ni, and/or Mn hydroxide product,followed by thermal dehydration to produce a Co, Ni, and/or Mn oxideproduct (e.g., cobalt (II, III) oxide, Co₃O₄, nickel (II) oxide, NiO,manganese (IV) dioxide, MnO₂). The Co, Ni, and/or Mn product thenreports to solid-liquid separation, and a solid filter cake iscollected. If the Co, Ni, and/or Mn-containing filter cake is leachedwith sulfuric acid, the leachate can then report to an evaporativecrystallizer, and the resulting product will consist of a mixture ofcobalt sulfate heptahydrate/CoSO₄.7H₂O, nickel sulfatehexahydrate/NiSO₄.6H₂O, and manganese sulfate mononydrate/MnSO₄.H₂O. Thecrystallized slurry then reports to, for example, solid-liquidseparation (e.g., centrifuge or filter press), followed by a drier todrive off excess water.

Alternatively, Al and/or Fe-depleted solution (Al and/or Fe productpreparation filtrate) is reacted with an oxidant (e.g. hydrogenperoxide) and a base may be added to maintain the pH between 5 and 7 toproduce a manganese dioxide precipitate which is removed usingsolid-liquid separation (e.g. a filter press). Cobalt is then optionallyselectively extracted from the filtrate into a cobalt rich stream, whichis then stripped washed and crystalized to form a cobalt sulfateheptahydrate product. The filtrate is then reacted with additionalhydroxide (e.g., sodium hydroxide, hydrated lime/calcium hydroxide,etc.) to precipitate nickel/nickel-cobalt hydroxide. The precipitate isremoved via solid liquid filtration.

According to parameters as outlined in the appended Tables belowrelating to exemplary Process 2 conditions, sodium sulfate is isolatedas a salt by-product prior to lithium recovery, utilizing the Co, Ni,and/or Mn solid-liquid separation filtrate. The filtrate is crystallizedto produce sodium sulfate decahydrate. This crystallization is achievedby cooling the sodium sulfate solution in a crystallizer, such as drafttube baffle crystallizers, following which the crystals undergosolid-liquid separation (e.g. via a centrifuge or filter press), and theisolated solid crystals are optionally dried and cooled. Subsequently,the filtrate from the solid-liquid separation of the isolated crystalsreport to lithium recovery.

The sodium sulfate solid-liquid separation filtrate is then reacted witha carbonate (e.g., sodium carbonate, etc.) to precipitate lithiumcarbonate/Li₂CO₃. This lithium carbonate product optionally undergoessolid-liquid separation (e.g., centrifugation) and a solid cake iscollected. To optionally further purify the lithium carbonate, itreports to an ion exchange column to remove trace impurities such ascalcium and magnesium (see, for example, Table 12); and then, to abicarbonation circuit where carbon dioxide is bubbled into, for example,a dissolution/digestion tank to convert the lithium carbonate into moresoluble lithium bicarbonate before being recrystallized into a higherpurity lithium carbonate slurry. The slurry is then solid-liquidseparated to give high purity lithium carbonate/Li₂CO₃ and is optionallydried.

Alternatively, the sodium sulfate solid-liquid separation filtrate isreacted with a hydroxide (e.g., sodium hydroxide, hydrated lime/calciumhydroxide, etc.) to form a lithium hydroxide and sodium sulfatesolution. The lithium hydroxide and sodium sulfate solution reports tocrystallization (e.g. using a draft tube baffle crystallizer) to coolthe solution and produce a slurry including sodium sulfate decahydratecrystals and soluble lithium hydroxide. The slurry from crystallizationreports to solid-liquid separation (e.g. using centrifugation) toseparate a solid sodium sulfate decahydrate product and a filtratecomprising lithium hydroxide in solution. The lithium hydroxide solutionfrom solid-liquid separation is evaporative crystallized: the lithiumhydroxide monohydrate is crystallized using, for example, a tripleeffect crystallizer; then, solid-liquid separated via, for example,centrifugation. The product is optionally further purified by dissolvingthe lithium hydroxide monohydrate crystals in pure water (e.g.,distilled or deionized water) and recrystallizing them (e.g. using amechanical vapour recompression (MVR) crystallizer), followed byoptional solid-liquid separation (e.g. using a centrifuge) to collectthe purified lithium hydroxide monohydrate product. The lithiumhydroxide monohydrate crystals are optionally dried.

Sodium sulfate is optionally isolated as a product. In one embodiment,the centrate from the Li₂CO₃ solid/liquid separation (e.g.,centrifugation) optionally reports to an evaporative crystallizer toproduce sodium sulfate decahydrate/Na₂SO₄.10H₂O. Sulfuric acid isoptionally added during said crystallization to convert any residualcarbonate (e.g. Na₂CO_(3(aq))) into a sulfate form. The resultingcrystallized slurry is solid-liquid separated (e.g., centrifuged), andthe separated solid product reports to a drier (e.g., a flash drier).The drier drives off water and produces anhydrous sodium sulfate/Na₂SO₄.

Table 12 delineates example design parameters; and Table 13 delineateskey reaction chemistry for the Phase 3 final product preparation steps,per the IDEAS process simulation mode results.

Example 3—Validation of Process 2

Size reduction of lithium-ion batteries was conducted as outlined inExample 5 below, dry magnetic separation was conducted to separate thescrap steel (magnetic product stream) from the rest of the material(non-magnetic feed stream). The non-magnetic feed stream was thenstripped by mixing at 10 wt % with N-Methyl-2-pyrrolidone (NMP) as astripping solvent at 80° C. for 6 hours to release the cathode and anodefrom their substrates which are made of aluminum (Al) and copper (Cu)foils. The stripped slurry stream was passed through a 500 μm screen toseparate the undersize stripped slurry stream containing fine cathodeand anode material and the liquid organic solvent (i.e. strippingsolvent) from the oversize solids portion containing Al, Cu, and plasticpieces of the substrate. The oversize solids portion was subjected todensity (densimetric) separation to separate the Al, Cu, and plasticfrom each other. The plastic was separated using a liquid with aspecific gravity (SG) of 2.5 which was followed by the separation ofaluminum from the copper using a liquid with an SG of 2.85. Theundersize stripped slurry stream containing the fine cathode and anodematerial was separated from the liquid organic (stripping) solvent usinga Buchner funnel with a Whatman® grade 541 filter paper attached to avacuum flask.

Leaching of the fine cathode and anode material (i.e. black mass solidstream) was conducted with a pulp density of 10% in 0.5M sulfuric acid(H₂SO₄) for 6 hours at 80° C. The leach solution was maintained at a pHof 2.5 via addition of H₂SO₄ over the course of the reaction time.Hydrogen peroxide (H₂O₂) was added throughout the leach to promotecobalt (Co) leaching. The leaching resulted in the recovery of 95% ofall of the metals processed in the product streams—i.e. 95% of the Cu,Al, Fe, Co, Ni, Mn, and Li were found to be leached from the black massinto the pregnant leach solution. The pregnant leach solution (PLS) wasseparated from the residual solids using a Buchner funnel with aWhatman® grade 3 filter paper attached to a vacuum flask. The residualsolids (corresponding to the 1^(st) product stream in FIG. 1B) weremixed with water and the slurry adjusted to pH 5 and then processed in a2-stage flotation circuit to produce a graphite product. The first stagewas a rougher flotation from which the overflow was processed in acleaner flotation.

The PLS (corresponding to the 2^(nd) product stream in FIG. 1B) was thenadjusted to pH 2 using 50 wt % sodium hydroxide (NaOH) in preparationfor copper (Cu) removal. The Cu was removed using solvent extraction; anorganic extractant, LIX 984N, at 30 vol % diluted in kerosene was mixedwith the PLS. The Cu was loaded onto the organic phase while the aqueousphase, the raffinate (corresponding to the 3^(rd) product stream in FIG.1B), continued to the next process step. The Cu was stripped from theorganic phase using 1M H₂SO₄ where it was sent to electrowinning for theproduction of copper plating.

Following the Cu removal, the raffinate was adjusted to pH 4.5 at 50° C.by the addition of 50 wt % NaOH which resulted in the precipitation ofiron (Fe) and Al as hydroxides, Fe(OH)₃ and Al(OH)₃. The solution wasseparated from the precipitate using a Buchner funnel with a Whatman®grade 3 filter paper attached to a vacuum flask. The filtered solidswere then washed in warm (50° C.) water and filtered a second time usingthe same procedure as previously stated. The solids were dried in anoven at 80° C. The precipitation had a recovery of >99% and produced amixed hydroxide product with a purity of 85%.

The filtrate (corresponding to the 4th product stream in FIG. 1B) wasadjusted to pH 9.5 at 50° C. by the addition of 50 wt % NaOH whichresulted in the precipitation of cobalt (Co), nickel (Ni), and manganese(Mn) as hydroxides, Co(OH)₂, Ni(OH)₂, and Mn(OH)₂. The solution wasseparated from the precipitate using a Buchner funnel with a Whatman®grade 3 filter paper attached to a vacuum flask. The filtered solidswere then washed in warm (50° C.) water and filtered a second time usingthe same procedure as previously stated. The solids were dried in anoven at 80° C.

The filtrate (corresponding to the 5^(th) product stream in FIG. 1B) wasevaporated to reduce the volume to a point when the sodium (Na)concentration reached a concentration of 70 g/L. Evaporation wasconducted at 95° C. The solution was then adjusted to pH 9.5 using 50 wt% NaOH. The solution was then mixed and was cooled to 10° C. and sodiumsulfate decahydrate (Na₂SO₄.10H₂O) precipitated from the solution. Thesolution was separated from the precipitate using a Buchner funnel witha Whatman® grade 3 filter paper attached to a vacuum flask. The filteredsolids were then washed in a basic, pH 9.5, solution and filtered asecond time using the same procedure as previously stated. The solidswere then dried under vacuum to produce anhydrous sodium sulfate(Na₂SO₄).

The filtrate (corresponding to the 6th product stream in FIG. 1B) wasevaporated to reduce the volume to a point when the lithium (Li)concentration reached a concentration of 11 g/L. A saturated sodiumcarbonate (Na₂CO₃) solution was prepared with as concentration of 430g/L and heated to 90° C. The Na₂CO₃ solution was added to the filtratesuch that the carbonate (CO₃ ²⁻) was 1.25 times the stoichiometricrequirement to precipitate the Li. The mixture of the filtrate andNa₂CO₃ was mixed at 95° C. for 6 hours. The solution was separated fromthe precipitate using a Buchner funnel with a Whatman® grade 3 filterpaper attached to a vacuum flask. The filtered solids were then washedin hot (70° C.) water and filtered a second time using the sameprocedure as previously stated. The solids were dried in an oven at 80°C. The precipitation had a recovery of 90% and produced a crude Li₂CO₃product with a purity of 89% to be later purified.

The Na₂SO₄ process was repeated to remove the remaining Na₂SO₄ from thefiltrate.

Example 4—Exemplary System/Apparatus

FIG. 2 is a schematic illustration in accordance with an exemplaryembodiment of the apparatus and system of the present application. FIG.2 illustrates an apparatus 1 for carrying out size reduction of batterymaterials under immersion conditions comprising a housing 2 configuredto hold an immersion liquid 4, a first feed chute 6 (hopper) having anopening 8 disposed therein for receiving battery materials of a firsttype 10 into the housing 2, a first submergible comminuting device 12disposed within the housing 2 to receive battery materials of a firsttype 10 from first feed chute 6 to cause a size reduction of batterymaterials of a first type 10 and form a first reduced-size batterymaterial 14, and a second submergible comminuting device 16 disposedwithin housing 2 to receive the first reduced-size battery material 14from first submergible comminuting device 12 and cause a further sizereduction in the first reduced-size battery material 14 to form a secondreduced-size battery material 18. A second reduced-size battery material18 can exit the apparatus as an exit stream of materials in a direction,for example, as indicated by the arrow in FIG. 2, and/or be furtherreceived and processed by additional downstream apparatuses and/orsystems and/or processes. In this exemplary embodiment, batterymaterials of the first type 10 are large format rechargeable lithium-ionbatteries as described above (e.g., lithium-ion batteries measuringapproximately up to 5000 mm×2000 mm×1450 mm in size or electric carbatteries). The first reduced-size battery material 14 in the exemplaryembodiment shown has a particle size smaller than about 400 mm. In thisexemplary embodiment, the first submergible comminuting device 12 andthe second submergible comminuting device 16 are multi-shaft shredders.

Referring to FIG. 2, there is provided a first feed chute 6 to deliverbattery materials of a first type 10 to a first submergible comminutingdevice 12 for forming a first reduced-size battery material 14. Asubmergible conveyor 22 is provided for receiving and delivering a firstreduced-size battery material 14 to a second submergible comminutingdevice 16 for forming a second reduced-size battery material 18. Thesecond reduced-size battery material 18 in the exemplary embodimentshown has an particle size smaller than about 100 mm. In the schematicshown in FIG. 2, the submergible conveyor 22 is a self-cleaning chainconveyor having a collection element 21 that is a pipe, wherein the pipedefines an open side or slot opposite from the underside of thesubmergible conveyor, thus allowing undersized materials to fall throughthe opening/slot and collect in the pipe. These undersized materials canbe suctioned or pumped to downstream apparatuses/systems/processes.

Referring to FIG. 2, there is provided a second feed chute 24 (hopper)having an opening 26 disposed therein for receiving battery materials ofa second type 28 into the housing 2. In the schematic shown in FIG. 2,the housing 2 comprises a delivery chute 27 for delivering the batterymaterials of the second type 28 from the second feed chute 24 directlyto the second submergible comminuting device 16. The second submergiblecomminuting device 16 is configured to cause a size reduction in thefirst reduced-size battery material 14 as well as the battery materialsof a second type 28. In this exemplary embodiment, the battery materialsof a second type 28 are small format rechargeable lithium-ion batteriesas described above. In this exemplary embodiment, the battery materialsof a second type 28 are of a reduced size relative to battery materialsof a first type 10.

The apparatus further comprises an outlet for discharging comminutedmaterial produced by the second submergible comminuting device 16, inthe vicinity of the output of the second submergible comminuting device16, wherein the discharged comminuted material 18 can report to one ormore further optionally submergible comminuting devices, and/or tofurther downstream systems and processes.

FIG. 2 also illustrates an exemplary system 100 for carrying out sizereduction of battery materials under immersion conditions comprisingcomponents as described in respect of the apparatus 1 outlined above incombination with an immersion liquid 4. System 100 comprises a firstsubmergible comminuting device 12 for receiving battery materials of afirst type 10 and causing a reduction in size thereof to form a firstreduced-size battery material 14, a second submergible comminutingdevice 16 for receiving a first reduced-size battery material 14 andcausing a further reduction in size thereof to form a secondreduced-size battery material 18, and an immersion liquid 4 forsubmerging therein each of the first submergible comminuting device 12,the second submergible comminuting device 16, the first reduced-sizebattery material 14 and the second reduced-size battery material 18. Inthis exemplary embodiment, battery materials of the first type 10 arelarge format rechargeable lithium-ion batteries as described above. Thefirst reduced-size battery material 14 in the exemplary embodiment shownin FIG. 2 has a particle size smaller than about 400 mm.

Referring to FIG. 2, exemplary system 100 comprises a submergibleconveyor 22 for delivering a first reduced-size battery material 14 froma first submergible comminuting device 12 to a second submergiblecomminuting device 16, wherein each of the first submergible comminutingdevice 12, the second submergible comminuting device 16, the firstreduced-size battery material 14 and the second reduced-size batterymaterial 18 and the submergible conveyor 22 are submerged in animmersion liquid 4. In this exemplary embodiment, the submergibleconveyor 22 is a self-cleaning chain conveyor as described above and thesecond reduced-size battery material 18 has a particle size smaller thanabout 100 mm.

In the schematic shown in FIG. 2 of exemplary system 100, a firstsubmergible comminuting device 12 causes a size reduction in a batterymaterial of a first type 10 via shearing to form a first reduced-sizebattery material 14, and a second submergible comminuting device 16causes a further size reduction in the first reduced-size batterymaterial 14 via shearing to form a second reduced-size battery material18 that is submerged in the immersion liquid 4. In this exemplaryembodiment, each of a first submergible comminuting device 12 and asecond submergible comminuting device 16 is a multi-shaft shredder asdescribed above.

Referring to FIG. 2, exemplary system 100 comprises a first deliverysystem 30 for delivering battery materials of a first type 10 to a firstsubmergible comminuting device 12. A first delivery system 30 in theschematic shown in FIG. 2 comprises a first feed chute 6 (hopper) andfor delivering the battery materials of the first type 10 to the firstsubmergible comminuting device 12. Exemplary system 100 in the schematicshown in FIG. 2 further comprises a second delivery system 32 configuredfor delivering battery materials of a second type 28 directly to asecond submergible comminuting device 16 to form a comminuted material34 submerged in an immersion liquid 4. The comminuted material 34combines with the second reduced-size battery material 18 and is of asimilar size. The second delivery system 32 comprises a second feedchute 24 and delivery chute 27. In this exemplary embodiment, batterymaterials of a second type 28 are small format lithium-ion batterieswhich are of a reduced size relative to battery materials of a firsttype 10 which are large format lithium-ion batteries.

Referring to FIG. 2, exemplary system 100 can comprise a thirdcomminuting device (not shown) to receive the comminuted batterymaterials (18/34) from the second submergible comminuting device 16,wherein the third comminuting device is optionally submergible inimmersion liquid 4 and causes a size reduction of the comminuted batterymaterials (18/34) received from the second submergible comminutingdevice 16. The comminuted material exiting the second submergiblecomminuting device 16 thus may be further processed via additionaldownstream systems and/or processes. For example, a third comminutingdevice may be integrated with other systems for further processing offurther comminuted battery materials. The system can further comprise afourth comminuting device to receive comminuted battery materials fromthe third optionally submergible comminuting device, as described abovein respect of the apparatus.

Table 14 provides the mechanical design criteria for an embodiment of anapparatus/system for carrying out size reduction of battery materialsunder immersion conditions.

Example 5—Physical Validation of System/Apparatus

A pilot test for battery material size reduction was carried out using amodified Franklin-Miller Taskmaster TM8500 Shredder™ shown in FIGS.3(a), 3(b), and 3(c) to size-reduce cylindrical lithium-ion batteriesvia shredding/shearing.

FIG. 3(a) is a picture of the modified Franklin-Miller Taskmaster TM8500Shredder™, which is a dual shaft shredder that has been modified tooperate under immersion conditions. As can be seen from FIG. 3(a), themodified shredder comprises a feed chute (hopper) for feeding batteriesinto the system/apparatus, a drive portion (motor) operatively coupledto a comminuting portion for shredding the batteries, and an immersiontank disposed below the comminuting portion which together with thecomminuting portion of the shredder forms a housing for containing animmersion liquid. The feed chute/hopper has been modified from theoriginal factory specifications to make it somewhat shorter. Inaddition, water-tight seals have been added around the drive shaft aswell as the area where the feed chute/hopper is connected to thecomminuting portion, to prevent leakage of immersion liquid into thedrive shaft (motor) portion of the shredder, as well as to preventleakage of immersion liquid to the exterior of the shredder. Theimmersion tank includes a drain for draining the immersion liquidfollowing comminution. FIG. 3(b) is a picture of the control andelectrical panel for the modified Franklin-Miller Taskmaster TM8500Shredder™ shown in FIG. 3(a). FIG. 3(c) is a picture of the comminutingportion of the modified Franklin-Miller Taskmaster TM8500 Shredder™shown in FIG. 3(a). FIG. 3(d) is a picture of the comminuting portion ofthe modified Franklin-Miller Taskmaster TM8500 Shredder™ shown in FIG.3(a) showing the comminuting portion immersed in the immersion liquid.

For the pilot test, fully charged lithium-ion batteries were firstimmersed and discharged in a 10% NaCl solution. The batteries testedwere small format, cylindrical Nickel-Manganese-Cobalt (NMC) chemistrylithium-ion batteries and Nickel-Cobalt-Aluminum (NCA) chemistrylithium-ion batteries, having approximate dimensions of 69.6 mm×18.1 mm,and a mass of approximately 50 g. An immersion liquid was prepared byadding Ca(OH)₂ to a solution until the solution pH measuredapproximately 12. Batches of 10 lithium-ion batteries were then shreddedin a 31 L volume of immersion liquid which was poured into the immersiontank and submerged the comminuting portion of the shredder. Noappreciable amount of dust or gas from battery size reduction wasproduced during the pilot test, which confirmed that the disclosedapparatuses and systems as herein described provides particularadvantages over known size reduction apparatuses and systems.

The shredded product shown in FIG. 4(a) was tested for fluorideconcentration using an ion probe. Results from the analysis showed anaverage of 1.3 to 3.4 ppm aqueous fluoride concentration depending onwhat type of battery was shredded (1.3 for nickel-manganese-cobalt/NMCbatteries and 3.4 for nickel-cobalt-aluminum/NCA). A separate batch of20 NCA batteries were shredded in the same solution volume as the firstbatch. The shredded product was also analyzed and had an aqueousfluoride concentration of 5.74 ppm. This low fluoride concentration is agood indicator that the fluoride level can be managed through Ca(OH)₂addition to the neutralizing solution.

As shown in FIG. 4(a), the battery material exiting the submergedshredder had an average particle size of approximately 40 mm with asingle pass through the shredder, which is representative of theexpected output from the second submergible comminuting device inaccordance with an embodiment of the present application. A fraction ofthe battery material exited the shredder as a layered battery materialhaving unliberated lithium-ion battery internals consisting of multiplelayers of cathode, cathode foil, separator, anode, and anode foilattached to the steel casing exterior. The shredded battery material wasseparated into large, small, and fine particle size fractions, the largeparticle size fraction comprising the layered battery material shown inFIG. 4(a). The layered battery material as shown in FIG. 4(a) was thenshredded in the shredder a second time, which liberated the layeredlithium-ion battery internals to yield particles having an average sizeof approximately 8 mm or less as shown in FIG. 4(b).

The combined small particle size fraction (from original separation andresulting from shredding of large particle size fraction) was granulatedin a dry granulator (Econogrind unit), which yielded a battery materialhaving a further reduced average particle size as shown in FIG. 4(c).The fine particle material noted above was screened from the large andsmall particle fractions via a wire mesh screen with 500 μm openingswhich was then filtered as shown in FIG. 4(d). The fine particlematerial was kept to be combined with the black mass material prior toleaching.

While batteries were first immersed and discharged in a 10% NaClsolution, prior to comminution of the batteries in a solution ofCa(OH)₂, a person skilled in the art would understand that the sameimmersion liquid could be used both for discharging and comminuting.Other options for immersion liquids are outlined in the sections above.

TABLE 1 Potential forecast of small and large format spent Li-ionbattery components, 2025 and 2030 Small Format Large Format Li-ionBattery Li-ion Battery Packs-e.g. Packs-e.g. NMC, LCO cathode LFP, LMO,NCA chemistry cathode chemistry wt % of total wt % of total battery packbattery pack Component 2025 2030 2025 2030 Steel — —  1.4%  1.4%Plastic-e.g. PP, PE, PET, 23.9% 23.9%  6.0%  6.0% PVDF ElectricalComponents  0.1%  0.1%  1.1%  1.1% Copper Cable — —  1.1%  1.1% Cellsand Enclosures Aluminum-Cathode Foil,  3.0%  3.0% 19.0% 19.0% ModuleCasing Copper-Anode Foil  9.0%  9.0%  9.9%  9.9% Electrolyte Lithium 0.1%  0.1%  0.1%  0.1% Phosphorous  0.3%  0.3%  0.4%  0.4% Fluorine 1.0%  1.0%  1.3%  1.3% Organic (e.g. ethylene  8.7%  8.7% 11.7% 11.7%carbonate/EC mixed with ethyl methyl carbonate/EMC) Electrode PowderAnode-Graphite 26.0% 26.0% 15.0% 15.0% Cathode-blended forecast Aluminum— —  0.4%  0.4% Cobalt 16.9% 16.9%  5.5%  5.3% Iron — —  3.2%  3.9%Lithium°  2.0%  2.0%  1.2%  1.2% Manganese — —  7.1%  6.1% Nickel — — 5.5%  5.3% Oxygen  9.2%  9.2%  8.3%  8.6% Phosphorous — —  1.8%  2.2%TOTAL 100% 100% 100% 100%

TABLE 2 Example design and IDEAS process simulation parameters for Phase1 feed size reduction steps according to Processes 1 and 2 Source/ StepParameter Unit Criteria Comment Discharging Percent of full charge % 20%Initial basis of at receipt/start Large of processing Format Dischargedvoltage V 1.0-2.0 Initial basis. Batteries of large format To ensureLi-ion batteries safe size reduction downstream Crusher/ Rotation Speedrpm 10-20 Shredder Blade Type — Cross-cut angled blades Immersion type —Make-up — process water/brine Example maximum ° C. 60 Example exittemperature of maximum water temperature for safe dismantling Wateraddition rate m³  2 To fully water/m³ immerse feed feed spent Li-ionLi-ion batteries batteries Screening Undersized fraction mm ≤10 Oversized fraction mm ≤100 to ≥10 Filtration of Solids in filtrateg/L >2   undersize Filter cake discharge % w/w 20% fraction moisturefrom Wash ratio t/t solids >0.5 screening Wash water addition t/h Variedto rate achieve wash ratio Overall wash % 98% efficiency Shredding Inletsize fraction mm ≤100 to ≥10 Oversize fraction from screening RotationSpeed rpm >50  To ensure shredding to targeted size Exit size fractionmm ≤10 

TABLE 3 Example design and IDEAS process simulation parameters for Phase2 magnetic separation and eddy current separation of Process 1 StepParameter Unit Example Criteria Rougher Type — Wet low intensitymagnetic and optional separator Cleaner Mechanical availability % 98%Magnetic Drum operating speed rpm <50 Separator(s) Separation type —Equipment supplier to recommend. Likely concurrent design, based onexpected coarseness of the mag fraction Magnetic field intensity At drumsurface gauss Equipment supplier to advise; likely ~1000 50 mm from drumgauss Equipment supplier to advise; surface likely ~400 Drive type —Motor Shredded Vibration type — Linear Steel Vibration drive — ElectricDewatering Shredded steel product % <1%  Screen moisture content Bedangle — ≤5 deg. to ≥5 deg. Eddy Rotor type — Concentric rotor CurrentFeed size mm ≤10 Separation Ferrous metal % >95% separation efficiencyNon-ferrous metal % >95% recovery Inert stream recovery % >95% AluminumVibration type — Linear Dewatering Vibration drive — Electric ScreenShredded aluminum % <1%  product moisture content Bed angle — ≤5 deg. to≥5 deg.

TABLE 4 Example design and IDEAS process simulation parameters for Phase2 leaching, and CCD of Process 1. Step Parameter Unit Example CriteriaLeaching Acid (e.g., H₂O₄) m³ Stoichiometric + addition rate excessExcess acid % 10% (e.g., H₂SO₄) relative to stoichiometric amount Acid(e.g., H₂SO₄) mol/L 1-2 reagent concentration H₂O₂ addition rate m³Stoichiometric H₂O₂ reagent g/L 20-30 concentration Temperature Range °C. 60-95 Pressure kPa Ambient Target pH pH Per stoichiometry, dependenton input cathode chemistry Agitation type — High shear Residence/ min.120-180 Leaching Time Optional Oxygen m3/hour Stoichoimetric + AdditionRate excess Screen Undersize fraction mm ≤5 Oversize fraction mm ≥5Countercurrent Wash ratio t process 2 Decantation water/t leached slurrySoluble losses %   1% Temperature ° C. Per inlet leached product andheat transfer over CCD train Pressure kPa Ambient Target pH — Per inletleached product, combined with wash water Final underflow % w/w ~30%suspended solids concentration Thickener type — High density thickener

TABLE 5 delineates reaction chemistry for the Phase 2 leaching step perthe IDEAS process simulation parameters of Process 1 and Process 2.Possible Extent of Metal

Extent of Reaction Source Leaching Reaction Chemistry

Category Reaction^([1]) Source NMC 6LiNi_(1/3)Mn_(1/3)Co_(1/3)O_(2(s)) +9H₂SO_(4(aq)) +

Targeted 95% (Wang, Vest, cathode H₂O_(2(aq)) →

& Friedrich, 2MnSO_(4(aq)) + 2NiSO_(4(aq)) + 2CoSO_(4(aq)) +

2011)⁽³⁾ 3Li2SO_(4(aq)) + 2O_(2(g)) + 10H₂O_((l)) LCO 2LiCoO_(2(s)) +3H₂SO_(4(aq)) + H₂O_(2(aq)) → Targeted 95% (Wang, Vest, cathodeLi₂SO_(4(aq)) + 2CoSO_(4(aq)) +O_(2(g)) + 4H₂O_((l)) & Friedrich,2011)⁽³⁾ LFP 2LiFePO_(4(s)) + 4H₂SO_(4(aq)) + H₂O_(2(aq)) → Targeted 5%(Wang, Vest, cathode^([2]) Li₂SO_(4(aq)) + Fe₂(SO₄)_(3(aq)) +2H₃PO_(4(aq)) + Friedrich, 2H₂O_((l)) 2011; Zou, 2012)^([2],[3]) LMO2LiMn₂O_(4(s)) + 5H₂SO_(4(aq)) + H₂O_(2(aq)) → Targeted 98% (Wang, Vest,cathode Li2SO_(4(aq)) + 4MnSO_(4(aq)) + 2O_(2(g)) + & Friedrich,6H₂O_((l)) 2011)^([3]) NCA 40LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2(s)) +(Wang, Vest, cathode 61H₂SO_(4(aq)) + H₂O_(2(aq)) → Targeted 95% &Friedrich, 20Li₂SO_(4 (aq)) + 32NiSO_(4(aq)) + 2011)^([3])6CoSO_(4(aq)) + Al₂(SO4)_(3(aq)) + 10O_(2(g)) + 62H₂O_((l)) Cu⁰, Cu⁰_((s)) + H₂SO_(4(aq)) + H₂O_(2(aq)) → Targeted 50%-95% (Wang, Vest,residual CuSO_(4(aq)) + 2H₂O_((l)) & Friedrich, copperfoil 2011)^([3])and cable Al⁰, 2Al⁰ _((s)) + 3H₂SO_(4(aq)) + 3H₂O_(2(aq)) → Side 60%-95%(Wang, Vest, residual Al₂(SO₄)_(3(aq)) + 6H₂O_((l)) & Friedrich,aluminum 2011)^([3]) foil and casing LiPF₆, 2LiPF_(6(aq)) +H₂SO_(4(aq)) + H₂O_(2(aq)) → Targeted 95% (Wang, Vest, electrolyteLi₂SO_(4(aq)) + 2HPF_(6(aq)) + H₂O_((l))) + & Friedrich, salt ½ O₂ (g)2011)^([3]) LiPF_(6(aq)) + H₂O_((l)) → Side 60% (Xu, 2004)^([4])HF_((aq)) + PF_(5(aq)) + LiOH_((aq)) Note 1: Extents of reaction arebased on IDEAS simulation model and literature extraction rates formetal oxides leached using sulfuric acid and hydrogen peroxide, per theoperating parameters in Table 4. [2]: H. Zou, Development of a RecyclingProcess, April 2012, Page 44 and IDEAS process simulation results, it islikely that minimal LiFePO₄ will be dissolved into solution due to thehigh bond energy between Fe and O, [3]: H. Wang, M. Vest, B. Friedrich,Proceedings of EMC 2011, 2011, Vol. 1, Pages 1-16. [4]: Z. Xu, ProcediaEnvironmental Sciences, 2012, Vol 16, Pages 443-450.

TABLE 6 Example design and IDEAS process simulation parameters for Phase2 intermediate product preparation of Process 1 Step Parameter UnitExample Criteria Agglomeration Flocculant type — Hydrophobic TankRougher Graphite recovery % w/w of influent >80% Flotation in rougherfroth Organic recovery % w/w of influent >80% in rougher froth Solublemetal % w/w of influent  <2% losses to froth Agitator type — Aerating,open flow Cell type — Conventional flotation Cleaner Graphite recovery %w/w of influent >80% Flotation in rougher froth Organic recovery % w/wof influent >80% in rougher froth Soluble metal % w/w of influent  <2%losses to froth Agitator type — Aerating, open flow Cell type —Conventional flotation Solid-liquid Solids in centrate g/L  0separation, e.g. Centrifuge cake % w/w ≥95% centrifugation solidscontent of cleaner froth Centrifuge wash t/t cake solid  1 ratio Numberof wash —  1 stages Temperature ° C. 20 of centrifuge wash water Washwater t/h Varied to addition rate achieve wash ratio Dual Media Firstmedia type — Anthracite Filtration Second media type — Garnet Outletorganic ppm >2  content in PLS Outlet suspended μm >10 solids size inPLS Optional- Organic adsorption % >95% Activated efficiency CarbonOperating Filtration Temperature ° C.  20

TABLE 7 Example design parameters for Phase 3 final product preparationof Process 1 Step Parameter Unit Example Criteria Solid-liquid Solids infiltrate g/L <0.5 filtration of Filter cake discharge % w/w ≤10% coppermoisture concentrate Wash ratio t/t solids 0.6 Wash water addition ratet/h Varied to achieve wash ratio Overall wash efficiency % 98% CopperIon Influent PLS copper g/L <1 Exchange (IX) concentration Cu ExtractionEfficiency % >95% Operating Temperature ° C. 20-40 Example resin type —LEWATIT ® M+ TP 207 Resin description — Weakly acidic, macroporouscation Regenerant — 10 wt % H₂SO₄ Regenerant rate (m³/h)/m²   5Conditioner, as required — 4 wt % NaOH Conditioner rate, as required(m³/h)/m²   5 Copper Copper IX eluate Cu content g/L ~10 electrowinning-(‘copper loaded liquor’) e.g. emew ® Conversion of inlet Cu_((aq))% >85% eluate content to Cu_((s)) Current density A/m² 250 Currentefficiency % 90% Copper plate product purity % 99.9% Co, Ni, and/orHydroxide (e.g., NaOH) L Stoichiometric Mn Hydroxide addition rate perbatch Precipitation Hydroxide (e.g., NaOH) mol/L   1 concentrationTemperature ° C.  40 Pressure kPa Ambient Target pH pH >10 ResidenceTime min.  60 Co, Ni, and/or Solids in filtrate g/L <0.5 Mn HydroxideFilter cake discharge % w/w 5% Solid-Liquid moisture Separation Washratio t/t solids 0.6 Wash water addition rate t/h Varied to achieve washratio Overall wash efficiency % 98% Crude Lithium Lithium carbonateg/100 g 2.5 Carbonate concentration in water Precipitation mother liquorSoda ash addition rate — Stoichiometric + excess Soda ash purity % w/w≥98.5% Excess soda ash — 10% Temperature ° C.  90 Crude Lithium Solidsin centrate g/L   0 Carbonate Centrifuge cake solids % w/w 87%Solid-Liquid content Separation, Centrifuge wash ratio t/t cake solid  1 E.g. Number of wash stages —   1 centrifugation Wash efficiency %90% Temperature of centrifuge wash water ° C.  90 Wash water additionrate t/h Varied to achieve wash ratio Centrifuge type — Peeler LithiumRecycle liquor addition rate t/h Varied to achieve Li Carbonateconcentration in Digestion digestion discharge Lithium concentration ing Li/L ~6.8 digestion discharge Carbon dioxide makeup t/h Varied basedon flow rate utilization and stoichiometry Carbon dioxide solubility g/Lwater 0.9 Carbon dioxide utilization %  95 (overall) Digestiontemperature ° C.  35 Impurity Ion Targeted trace impurities — Calciumand magnesium Exchange Ca and Mg extraction % <90% (IX) efficiencyOperating Temperature ° C. <80 Target pH — 3-4.5 Example resin type —Dow Amberlite ® IRC747 Resin description — Macroporous cation Regenerant— 1-2 N HCl Regenerant addition rate — Stoichiometric Reagent forconversion to — 1-2 N NaOH Na⁺ form Reagent for conversion to —Stoichiometric Na⁺ form addition rate Pure Lithium Lithium carbonateg/100 g 0.75 Carbonate concentration in inlet liquor waterCrystallization Carbon dioxide solubility g/L water 0.5 Steam additionrate (direct t/h Varied to achieve design steam injection) temperatureCrystallization temperature ° C.  95 Pure Lithium Solids in centrate g/L  0 Carbonate Centrifuge cake solids % w/w 87% Centrifugation contentCentrifuge wash ratio t/t cake   1 solid Number of wash stages —   1Wash efficiency % 90% Temperature of centrifuge ° C.  90 wash water Washwater addition rate t/h Varied to achieve wash ratio Centrifuge type —Peeler Lithium Natural Gas addition rate t/h Varied to achieve Carbonatedischarge temp. Drying and Combustion air addition rate t/h Varied totarget Cooling combustion gas O₂ Oxygen content in off-gas % v/v   3Dilution air addition rate t/h Varied to target off-gas solids Dryerdischarge solids % w/w   0 moisture Drier type — Flash drier Cooledproduct temperature ° C.  40 Flash dryer discharge ° C. 120 temperatureSodium Sulfuric acid addition rate t H₂SO₄/t Stoichiometric + excessSulfate feed Crystallization Excess H₂SO₄ relative to % 10%stoichiometry Sodium sulfate in crude LC % w/w ~6% centrate Solids incrystallizer slurry % w/w 25% discharge Operating pressure kPa 0.85-1Operating temperature ° C. 6-7 Crystallizer type — Draft tube withbarometric leg Sodium Solids loss to centrate (% of % 2% Sulfate Solid-feed solids) Liquid Centrifuge cake moisture % w/w 2% Separation,content e.g. Centrifuge wash ratio t/t cake 0.05 centrifugation solidNumber of wash stages —   1 Wash efficiency % 95% Wash water additionrate t/h Varied to achieve wash ratio Centrifuge type — Pusher SodiumNatural Gas addition rate t/h Varied to achieve Sulfate discharge temp.Drying Combustion air addition rate t/h Varied to target combustion gasO₂ Oxygen content in off-gas % v/v   3 Dilution air addition rate t/hVaried to target off-gas solids Dryer discharge solids % w/w   0moisture Drier type — Flash drier Cooled product temperature ° C.  40Flash dryer discharge ° C. 120 temperature

TABLE 8 Reaction chemistry for Phase 3 final product preparation, perIDEAS process simulation of Process 1 Possible Standard Extent ofElectrode Step Reaction Chemistry Category Reaction⁽¹⁾ Potential (V)Copper Ion 2Na—R—C₄H₇NO_(4 (s)) + CuSO_(4(aq)) → Targeted >95% —Exchange Cu(Na—R—C₄H₆NO₄ ⁻)_(2 (ag)) + H₂SO_(4(aq))2Na—R—C₄H₇NO_(4 (s)) + CuSO_(4 (aq)) → Side  10% — Cu(R—C₄H₇NO₄⁻)_(2(aq)) + Na₂SO_(4(aq)) Cu(R—C₄H₇NO₄ ⁻)_(2(aq)) + 2HCl_((aq)) →Regeneration 100% — Cu²⁺ _((ag)) + 2Cl⁻ _((aq)) + 2Na—R—C₄H₇NO_(4(s))Cu(R—C₄H₇NO₄ ⁻)_(2(aq)) + 2NaOH_((eq)) → Conditioning 100% — Cu²⁺_((aq)) + 2OH⁻ _((aq)) + 2Na—R—C₄H₇NO_(4(s)) Copper Cu²⁺ _((ag)) + 2e⁻ →Cu_((s)) Cathode 100% E° = 0.34 Electrowinning H₂O_((l)) → 2H⁺ _((aq)) +½O_(2(g)) + 2e⁻ Anode 100% E° = −1.23 (e.g. emewe ®) Cu²⁺ _((aq)) + H₂O→ 2H⁺ _((aq)) + ½O_(2(g)) + Cu_((s)) Overall 100% E° = 0.89 Co, Ni,and/or CoSO_(4(aq)) + 2NaOH_((aq)) → Targeted 100% — Mn Product,Co(OH)_(2(s)) + Na₂SO_(4(aq)) e.g. Hydroxide NiSO_(4(aq)) + 2NaOH_((aq))→ Targeted 100% — Precipitation Ni(OH)_(2(s)) + Na₂SO_(4(aq))MnSO_(4(aq)) + 2NaOH_((aq)) → Targeted 100% — Mn(OH)_(2(s)) +Na₂SO_(4(aq)) Li₂SO_(4(aq)) + 2NaOH_((aq)) → Side 0-5% — LiOH_((aq)) +Na₂SO_(4(aq)) Lithium Li₂SO_(4(aq)) + Na₂CO_(3(s)) → Targeted 100% —Carbonate Na₂SO_(4(aq)) + Li₂CO_(3(s)) Precipitation LithiumLi2CO_(3(s)) + H₂O_((l)) + CO_(2(g))→ Targeted 100% — Carbonate2LiHCO_(3(aq)) Digestion Impurity Ion R—CH₂—NH—CH₂—PO₃Na_(2(s)) +Targeted 100% — Exchange (IX) M²⁺ _((aq)) → R—CH₂—NH—CH₂—PO₃M_((ag)) +2Na⁺ _((ag)) R—CH₂—NH—CH₂—PO₃M_((ag)) + Regeneration 100% — 2HCl_((aq))→ M²⁺ _((aq)) + 2Cl⁻ _((aq)) + R—CH₂—NH—CH₂—PO₃H_(2(s))R—CH₂—NH—CH₂—PO₃H_(2(s)) + Conversion 100% — 2NaOH_((aq))→ to Na⁺ formR—CH₂—NH—CH₂—PO₃Na_(2(s)) + 2H2O_((l)) Pure Lithium 2LiHCO_(3(aq)) →Li₂CO_(3(s)) + CO_(2(g)) + Targeted 100% — Carbonate H₂O_((l))Precipitation Lithium H₂O_((I)) →H₂O_((g)) Targeted 100% — CarbonateNa₂SO_(4(aq)) → Na₂SO_(4(s)) Side 100% — Drying and Na₂CO_(3(aq)) →Na₂CO_(3(s)) Side 100% — Cooling Sodium Na₂SO_(4(aq)) + 10H₂O_((l))Targeted 100% — Sulfate Na₂SO₄ • 10H₂O_((s)) CrystallizationNa₂CO_(3(aq)) + H₂SO_(4(aq)) → Targeted 100% — Na₂SO_(4(aq)) +H₂O_((l)) + CO_(2(g)) Li₂CO_(3(aq)) + H₂SO_(4(aq)) → Targeted 100% —Li₂SO_(4(aq)) + H₂O_((l)) + CO_(2(g)) Li₂CO_(3(s)) + H₂SO_(4(aq)) →Targeted 100% — Li₂SO_(4(aq)) + H₂O_((l)) + CO_(2(g)) Sodium Na₂SO₄ •10H₂O_((s)) → Na₂SO_(4(aq)) + Targeted 100% — Sulfate Drying 10H₂O_((l))Na₂SO_(4(aq)) → Na₂SO_(4(s)) Targeted 100% — H₂O_((l)) → H₂O_((g))Targeted 100% —

TABLE 9 Example design and IDEAS process simulation parameters for Phase2 magnetic separation\ stripping, and optional densimetric separation ofProcess 2 Step Parameter Unit Example Criteria Rougher and Type —Wet/dry low intensity optional magnetic separator Cleaner Mechanicalavailability % 98% Magnetic Drum operating speed rpm <50 Separator(s)Separation type — Equipment supplier to recommend. Likely concurrentdesign, based on expected coarseness of the mag fraction Magnetic field— Equipment supplier to intensity recommend At drum surface gaussEquipment supplier to advise; likely ~1000 50 mm from drum gaussEquipment supplier to surface advise; likely ~400 Drive type — MotorShredded Vibration type — Linear Steel Vibration drive — ElectricDewatering Shredded steel %  <1% Screen product moisture content Bedangle — ≤5 deg. to ≥5 deg. Stripping Solvent type —n-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), ethyl acetate(EtOAc), isopropanol (IPA), acetone, dimethyl sulfoxide (DMSO), ordiethylfornnannide (DEF). Solvent addition rate m³ 1 solvent/ t influentsolids Densimetric Separation Efficiency % >95% Separation (Optional)Shredded Vibrational type — Linear Cu/Al/Plastics Vibration drive —Electric Dewatering Shredded steel product % <10% Screen moisturecontent Bed angle — −5 deg. to +5 deg. Distillation Distillation type —Vacuum

TABLE 10 Example design and IDEAS process simulation parameters forPhase 2 leaching of Process 2. Step Parameter Unit Example CriteriaLeaching Acid (e.g., H₂SO₄) m³ Stoichiometric + addition rate excessExcess acid (e.g., H₂SO₄) % 10% relative to stoichiometric amount Acid(e.g., H₂SO₄)) reagent mol/L 0.5-2  concentration 0.5 H₂O₂ addition ratem³ Stoichiometric H₂O₂ reagent concentration g/100 g of 20-30 feedTemperature Range ° C. 60-95  80 Pressure kPa Ambient Target pH pH Perstoichiometry, dependent on input cathode chemistry  2.5 Agitation type— High shear Residence/Leaching Time min. 120-180 360 Optional OxygenAddition m3/hour Stoichiometric + Rate excess Outlet Sulphate g/L 100Concentration Pulp Density % 10-30  10 Number of Tanks   3   1

TABLE 11 Example design and IDEAS process simulation parameters forPhase 2 intermediate product preparation of Process 2 Step ParameterUnit Example Criteria Rougher Graphite recovery % w/w >80% Flotation inrougher froth of influent Organic recovery % w/w >80% in rougher frothof influent Soluble metal losses to froth % w/w  <2% of influentAgitator type — Aerating, open flow Cell type — Conventional flotationCleaner Graphite recovery % w/w >80% Flotation in rougher froth ofinfluent Organic recovery % w/w >80% in rougher froth of influentSoluble metal % w/w  <2% losses to froth of influent Agitator type —Aerating, open flow Cell type — Conventional flotation Solid-liquidSolids in centrate g/L  0 separation, e.g. Centrifuge cake solids % w/w≥95% centrifugation content of Centrifuge wash ratio t/t cake solid  1cleaner froth Number of wash stages —  1 Temperature of centrifuge ° C.20 wash water Wash water addition rate t/h Varied to achieve wash ratioDual Media First media type — Anthracite Filtration Second media type —Garnet Outlet organic content in PLS ppm >2   Outlet suspended solidssize μm >10 in PLS Belt Filtration Solids in filtrate g/L >2  (Optional) Filter cake discharge % w/w 20% moisture Wash ratio t/tsolids >0.5 Wash water addition rate t/h Varied to achieve wash ratioOverall wash efficiency % 98% Activated Organic adsorption efficiency% >95% Carbon Operating Temperature ° C. 20 Filtration (Optional)

TABLE 12 Example design parameters for Phase 3 final product preparationof Process 2 Step Parameter Unit Example Criteria Copper Ion InfluentPLS copper g /L <1 Exchange (IX) concentration 0.8255 Cu ExtractionEfficiency % >95% Operating Temperature ° C. 20-40 Example resin type —DOWEX M4195 IX Resin description — Chelating, weak base Regenerant — 10wt % H₂SO₄ Regenerant rate (m³/h)/m² 5 Conditioner, as required — 4 wt %NaOH Conditioner rate, as required (m³/h)/m² 5 Copper Solvent InfluentPLS copper g/L >1 Extraction concentration 2.0925 (Optional) CuExtraction Efficiency % >95% Example extraction reagent — LIX 984NExample stripping reagent — H₂SO₄ Copper Copper IX eluate Cu content g/L~10 electrowinning- (‘copper loaded liquor’) e.g.emew ® Conversion ofinlet Cu_((aq)) eluate % >85% content to Cu_((s)) Current density A/m²250 Current efficiency % 90% Copper plate product purity % 99.9%Aluminum-Iron NaOH addition rate per batch L Stoichiometric hydroxideNaOH concentration mol/L 0.25 precipitation wt % 50 Temperature Range °C. 25-40 Pressure kPa Ambient Target pH pH 3-5 4.5 Aluminum-Iron Filtercake discharge moisture % w/w 0.5 precipitate Wash ratio t/t solids 0.6solid liquid Wash water addition rate t/h Varied to achieve washseparation ratio Overall wash efficiency % 98 Co, Ni, and/or Hydroxide(e.g., NaOH) addition L Stoichiometric Mn Hydroxide rate per batchPrecipitation Hydroxide (e.g., NaOH) mol/L 1 concentration wt % 50Temperature Range ° C. 40-60 Pressure kPa Ambient Target pH pH 8-10 9.5Residence Time min. 60 Co, Ni, and/or Solids in filtrate g/L <0.5 MnHydroxide Filter cake discharge moisture % w/w 5% Solid-Liquid Washratio t/t solids 0.6 Separation Wash water addition rate t/h Varied toachieve wash ratio Overall wash efficiency % 98% Sodium Sulfate Sulfuricacid addition rate t H2SO4/feed Stoichiometric + excess CrystallizationExcess H2SO4 relative to % 10% stoichiometry Sodium sulfateconcentration in g/100 g 40-45 PLS water 43.2 Solids in crystallizerslurry % w/w 25% discharge Operating pressure kPa 0.85-1 Operatingtemperature ° C. 100 95 Crystallizer type — Draft tube with barometricleg Sodium Sulfate Solids loss to centrate (% of % 2% Solid-Liquid feedsolids) Separation, e.g. Centrifuge cake moisture % w/w 2%centrifugation content Centrifuge wash ratio t/t cake solid 0.05 Numberof wash stages — 1 Wash efficiency % 95% Wash water addition rate t/hVaried to achieve wash ratio Centrifuge type — Peeler Sodium SulfateNatural Gas addition rate t/h Varied to achieve Drying discharge temp.Combustion air addition rate t/h Varied to target combustion gas O2Oxygen content in off-gas % v/v 3 Dilution air addition rate t/h Variedto target off-gas solids Dryer discharge solids moisture % w/w 0 Driertype — Flash drier Cooled product temperature ° C. 40 Flash dryerdischarge ° C. 120 temperature Crude Lithium Lithium sulphateconcentration g/L 200 Carbonate in PLS 174 Precipitation Soda ashaddition rate — Stoichiometric + excess Soda ash purity % w/w ≥98.5%98.5% Excess soda ash — 10% 25% Temperature ° C. 90 90 Crude LithiumSolids in centrate g/L 0 Carbonate Centrifuge cake solids content % w/w87% Solid-Liquid Centrifuge wash ratio t/t cake solid 1 Separation,Number of wash stages — 1 E.g. Wash efficiency % 90% centrifugationTemperature of centrifuge ° C. 90 wash water Wash water addition ratet/h Varied to achieve wash ratio Centrifuge type — Peeler LithiumRecycle liquor addition rate t/h Varied to achieve Li Carbonateconcentration in digestion Digestion discharge Lithium concentration ing Li/L ~6.8 digestion discharge Carbon dioxide makeup flow t/h Variedbased on utilization rate and stoichiometry Carbon dioxide solubilityg/L water 0.9 Carbon dioxide utilization % 95 (overall) Digestiontemperature ° C. 35 Impurity Ion Targeted trace impurities Calcium andmagnesium Exchange (IX) Ca and Mg extraction efficiency % <90% OperatingTemperature ° C. <80 Target pH — 3-4.5 Example resin type — DowAmberlite ® IRC747 Resin description — Macroporous cation Regenerant 1-2N HCl Regenerant addition rate — Stoichiometric Reagent for conversionto Na+ — 1-2 N NaOH form Reagent for conversion to Na+ — Stoichiometricform addition rate Pure Lithium Lithium carbonate g/100 g 0.75 Carbonateconcentration in inlet liquor water Crystallization Carbon dioxidesolubility g/L water 0.5 Steam addition rate (direct t/h Varied toachieve design steam injection) temperature Crystallization temperature° C. 95 Pure Lithium Solids in centrate g/L 0 Carbonate Centrifuge cakesolids content % w/w 87% Centrifugation Centrifuge wash ratio t/t cakesolid 1 Number of wash stages — 1 Wash efficiency % 90% Temperature ofcentrifuge ° C. 90 wash water Wash water addition rate t/h Varied toachieve wash ratio Centrifuge type — Peeler Lithium Natural Gas additionrate t/h Varied to achieve Carbonate discharge temp. Drying andCombustion air addition rate t/h Varied to target Cooling combustion gasO2 Oxygen content in off-gas % v/v 3 Dilution air addition rate t/hVaried to target off-gas solids Dryer discharge solids moisture % w/w  0 Drier type — Flash drier Cooled product temperature ° C.  40 Flashdryer discharge ° C. 120 temperature

TABLE 13 Reaction chemistry for Phase 3 final product preparation ofProcess 2, per IDEAS process simulation Possible Standard Extent ofElectrode Step Reaction Chemistry Category Reaction⁽¹⁾ Potential (V)Copper Ion 2Na—R—C₄H₇NO_(4(s)) + CuSO_(4(aq))→ Targeted >95% — ExchangeCu(Na—R—C₄H₆NO₄ ⁻)_(2(aq)) + H₂SO_(4(aq)) 2Na—R—C₄H₇NO_(4(s)) +CuSO_(4(aq))→ Side 10% — Cu(R—C₄H₇NO₄ ⁻)_(2(aq)) + Na₂SO_(4(aq))Cu(R—C₄H₇NO₄ ⁻⁾ _(2(aq)) + 2HCl_((aq)) → Regeneration 100% — Cu²⁺_((aq)) + 2Cl⁻ _((aq)) + 2Na—R—C₄H₇NO_(4(s)) Cu(R—C₄H₇NO₄ ⁻)_(2(aq)) +2NaOH_((aq)) → Conditioning 100% — Cu²⁺ _((aq)) + 2OH⁻ _((aq)) +2Na—R—C₄H₇NO_(4(s)) Copper Solvent CuSO_(4(aq)) + 2HR_((org)) →CuR_(2(org)) + H₂SO_(4(aq)) Extraction >95% — Extraction CuR_(2(org)) +H₂SO_(4(aq)) → CuSO_(4(aq)) + 2HR_((org)) Stripping >95% — (Optional)Copper Cu²⁺ _((aq)) + 2e⁻ → Cu_((s)) Cathode 100% E° = 0.34Electrowinning H₂O_((l)) → 2H⁺ _((aq)) + ½O_(2(g)) + 2e⁻ Anode 100% E° =−1.23 (e.g. emew ®) Cu²⁺ _((aq)) + H₂O → 2H⁺ _((aq)) + ½O_(2(g)) +Cu_((s)) Overall 100% E° = 0.89 Co, Ni, and/or CoSO_(4(aq)) +2NaOH_((aq)) → Co(OH)_(2(s)) + Na₂SO_(4(aq)) Targeted 100% — Mn Product,NiSO_(4(aq)) + 2NaOH_((aq)) → Ni(OH)_(2(s)) + Na₂SO_(4(aq)) Targeted100% — e.g. Hydroxide MnSO_(4(aq)) + 2NaOH_((aq)) → Mn(OH)_(2(s)) +Na₂SO_(4(aq)) Targeted 100% — Precipitation Li₂SO_(4(aq)) + 2NaOH_((aq))→ LiOH_((aq)) + Na₂SO_(4(aq)) Side 0-5% — Sodium Sulfate Na₂SO_(4(aq)) +10H₂O_((l)) → Na₂SO₄ • 10H₂O_((s)) Targeted 100% — CrystallizationNa₂CO_(3(aq)) + H₂SO_(4(aq)) → Na₂SO_(4(aq)) + H₂O_((l)) + CO_(2(g))Targeted 100% — Li₂CO_(3(aq)) + H₂SO_(4(aq)) → Li₂SO_(4(aq)) +H₂O_((l)) + CO_(2(g)) Targeted 100% — Li₂CO_(3(s)) + H₂SO_(4(aq)) →Li₂SO_(4(aq)) + H₂O_((l)) + CO_(2(g)) Targeted 100% — Sodium SulfateNa₂SO₄ • 10H₂O(s) → Na₂SO_(4(aq)) + 10H₂O_((l)) Targeted 100% — DryingNa₂SO_(4(aq)) → Na₂SO_(4(s)) Targeted 100% — H₂O_((l)) → H₂O_((g))Targeted 100% — Lithium Li₂SO_(4(aq)) + Na₂CO_(3(s)) → Na₂SO_(4(eq)) +Li₂CO_(3(s)) Targeted 100% — Carbonate Precipitation LithiumLi2CO_(3(s))+ H₂O_((l)) + CO_(2(g)) → 2LiHCO_(3(aq)) Targeted 100% —Carbonate Digestion Impurity Ion R—CH₂—NH—CH₂—PO₃Na_(2(s)) + M²⁺ _((aq))→ Targeted >95% — Exchange (IX) R—CH₂—NH—CH₂—PO₃M(_(aq)) + 2Na⁺ _((aq))R—CH₂—NH—CH₂—PO₃M_((aq)) + 2HCl_((aq)) → Regeneration 100% — M²⁺_((aq)) + 2Cl⁻ _((aq)) + R—CH₂—NH—CH₂—PO₃H_(2(s))R—CH₂—NH—CH₂—PO₃H_(2(s)) + 2NaOH_((aq)) → Conversion to 100% —R—CH₂—NH—CH₂—PO₃Na_(2(s)) + 2H2O_((l)) Na⁺ form Pure Lithium2LiHCO_(3(aq)) → Li₂CO_(3(s)) + CO_(2(g)) + Targeted 100% — CarbonateH₂O_((l)) Precipitation Lithium H₂O_((l)) → H₂O_((g)) Targeted 100% —Carbonate Na₂SO_(4(aq)) → Na₂SO_(4(s)) Side 100% — Drying andNa₂CO_(3(aq)) → Na₂CO_(3(s)) Side 100% — Cooling

TABLE 14 Mechanical design criteria for an embodiment of anapparatus/system for carrying out size reduction of battery materialsunder immersion conditions Step Parameter Unit Criteria Source/CommentOverall parameters Immersion Type — Make-up water Per mini-piloting withdilute Ca(OH)₂ program level Alternative — Make-up water Percommercial-scale Immersion Type with dilute NaCl design Alternative — Anorganic alkyl Per commercial-scale Immersion Type carbonate (e.g. designethylene carbonate) Optional aqueous wt. % 0.083 Per mini-pilotinghydrated lime program concentration Maximum 100 Maximum temperaturetemperature for safe dismantling Liquid Addition m³ liquid/m³ ≥ 2 Toensure full Rate feed immersion of li-ion spent li-ion batteriesbatteries Wetted material of — Austenitic stainless Materials compatibleconstruction steel (e.g. 304 with feed Stainless Steel) Self-cleaningConveyor type — Self-cleaning chain Per commercial-scale conveyorconveyor design Large format size Shredder Type — Quad Shaft Percommercial-scale reduction Shredder design Rotation Speed rpm 10-20 Lowrotation speed for initial mechanical separation Size of Output mm <400Per commercial-scale Solids design Self-cleaning Conveyor type —Self-cleaning chain Per commercial-scale conveyor conveyor design Coarseshredder Shredder Type — Twin or quadruple Per mini-piloting shaftprogram Rotation Speed rpm 30-40 Per mini-piloting program andcommercial-scale design Size of Output mm <100 Per mini-piloting Solidsprogram Optional-Fine Shredder Type — Twin or quadruple Percommercial-scale shredder shaft design Rotation Speed rpm 30-40 Size ofOutput mm >40 to <100 Solids Optional-Dry Shredder Type — Twin orquadruple Per commercial-scale shredder shaft design Rotation Speed rpm30-40 Size of Output mm <40 Solids

All publications, patents and patent applications mentioned in thisSpecification are indicative of the level of skill of those skilled inthe art to which this application pertains and are herein incorporatedby reference to the same extent as if each individual publication,patent, or patent applications were specifically and individuallyindicated to be incorporated by reference.

The present application being thus described, it will be obvious thatthe same may be varied in many ways. Such variations are not to beregarded as a departure from the spirit and scope of the presentapplication, and all such modifications as would be obvious to oneskilled in the art are intended to be included within the scope of thefollowing claims.

We claim:
 1. An apparatus for carrying out size reduction of batterymaterials under immersion conditions, the apparatus comprising: a) ahousing having a battery inlet through which battery materials can beintroduced into the housing; b) a comminuting apparatus disposed withinthe housing and configured to cause a size reduction of the batterymaterials to form reduced-size battery materials and to liberateelectrolyte materials and a black mass material comprising anode andcathode powders from within the battery materials; c) an immersionliquid within the housing and submerging the comminuting apparatus,whereby sparking caused by the size reduction of the battery material issuppressed and heat generated by the size reduction is absorbed by theimmersion liquid, and wherein the electrolyte materials, the black massmaterial and the reduced-size battery material are entrained within theimmersion liquid to form a sized-reduced feed stream; and d) a feedoutlet that is downstream from the comminuting apparatus through whichthe sized-reduced feed stream comprising the reduced-size batterymaterial, the black mass material and the electrolyte materialsentrained within the immersion liquid can exit the housing.
 2. Theapparatus of claim 1, further comprising a first separator that issubmerged by the immersion liquid and is disposed at the feed outlet toreceive the sized-reduced feed stream, the first separator configured toseparate the sized-reduced feed stream into at least: a) a black masssolid product stream comprising the black mass material and a retainedportion of the immersion liquid having entrained electrolyte materials;and b) a first filtrate stream comprising a second portion of theimmersion liquid having entrained electrolyte materials.
 3. Theapparatus of claim 2, wherein the retained portion of the immersionliquid having entrained electrolyte comprises up to 20% wt of the blackmass solid product stream.
 4. The apparatus of claim 2, wherein thefirst separator comprises a liquid-solid filter and wherein the firstfiltrate stream passes through the liquid-solid filter and the blackmass solid product stream comprises a filter cake material retained bythe liquid-solid filter.
 5. The apparatus of claim 4, wherein the firstseparator further comprises a screen in fluid communication between thefeed outlet and the liquid-solid filter, the screen being configured toseparate oversized solids from the sized-reduced feed stream before itreaches the liquid-solid separator while allowing the black massmaterial and the immersion liquid having entrained electrolyte materialsto pass through the screen.
 6. The apparatus of claim 5, wherein thescreen is configured to retain solids having a size that is greater thanabout 2 mm.
 7. The apparatus of claim 2, further comprising a recyclecircuit configured to recycle at least a first portion of the firstfiltrate stream into the immersion liquid within the housing, andfurther comprising an organic removal circuit in the recycle circuitbetween the first separator and the housing, wherein the organic removalcircuit is configured to separate at least some of the entrainedelectrolyte materials from the immersion liquid.
 8. The apparatus ofclaim 1, wherein the immersion liquid is basic and at least electricallyconductive.
 9. The apparatus of claim 1, wherein the immersion liquidreacts with hydrogen fluoride produced via the liberation of theelectrolyte materials during the size reduction, whereby the evolutionof hydrogen fluoride during the size reduction is inhibited.
 10. Theapparatus of claim 1, wherein the immersion liquid within the housing isat an operating temperature that is less than 70 degrees Celsius toinhibit chemical reactions between the electrolyte materials and theimmersion liquid.
 11. The apparatus of claim 10, wherein the operatingtemperature is less than 60 degrees Celsius.
 12. The apparatus of claim1, wherein the immersion liquid comprises at least one of water and anaqueous solution.
 13. The apparatus of claim 1, wherein the immersionliquid has a pH that is greater than or equal to
 8. 14. The apparatus ofclaim 1, wherein the immersion liquid comprises a salt whereby theimmersion liquid is electrically conductive to dissipate a residualelectrical charge within the battery materials that is released duringthe size reduction, and wherein the salt comprises at least one ofsodium hydroxide and calcium hydroxide.
 15. The apparatus of claim 1,wherein dust particles that are liberated from the battery materials bythe comminuting apparatus during the size reduction are captured andentrained within the immersion liquid and are inhibited from escapingthe housing into the surrounding atmosphere.
 16. The apparatus of claim1, wherein the comminuting apparatus comprises at least a firstcomminuting device that is submerged in the immersion liquid to receivethe battery materials.
 17. The apparatus of claim 16, wherein the firstcomminuting device comprises a shredder that is configured to cause sizereduction of the battery materials by at least one of compression andshearing.
 18. The apparatus of claim 1, wherein the comminutingapparatus further comprises a second comminuting device submerged withinimmersion liquid and being disposed downstream from the firstcomminuting device to receive the reduced-size battery material exitingthe first comminuting device and being configured to cause a second sizereduction of the battery materials to form further reduced-size batterymaterial and to liberate further electrolyte materials from within thebattery materials that are included in the sized-reduced feed stream,and wherein the second comminuting device is at a lower elevation thanthe first comminuting device, whereby the electrolyte materials and thereduced-size battery material that are entrained within the immersionliquid when exiting the first comminuting device flow into the secondcomminuting device.
 19. The apparatus of claim 19, wherein the batterymaterials comprise rechargeable lithium-ion batteries.
 20. The apparatusof claim 1, wherein the immersion liquid comprises at least one ofsodium hydroxide and calcium hydroxide.